Amino-functional polyesters containing urea, biuret, thiourea, dithiobiuret, thioamide, and/or amide moieties in their backbone and urethane/urea prepolymers and polymers made therefrom

ABSTRACT

This invention relates to novel polymeric polyamines containing internal urea, biuret, thiourea, dithiobiuret, amide, and/or thioamide moieties, and to polymers prepared therefrom. This invention also relates to novel isocyanate-functional prepolymers containing urea, biuret, thiourea, dithiobiuret, amide, and/or thioamide moieties and to polymers prepared therefrom.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of Ser. No. 247,460 filedSept. 21, 1988 now U.S. Pat. No. 4,916,201, which is acontinuation-in-part of Ser. No. 099,027, filed Sept. 21, 1987 nowabandoned, and is related to copending U.S. applications Ser. No.926,692, filed Nov. 5, 1986 now abandoned; Ser. No. 000,227, filed Jan.2, 1987 now U.S. Pat. No. 4,959,499; U.S. Pat. No. 4,689,353; U.S.application Ser. No. 254,503, filed Oct. 6, 1988, and Ser. No. 310,107,filed Feb. 10, 1989, by the same inventor.

BACKGROUND OF THE INVENTION

This invention relates to modified polyamines having backbonescontaining (1) polyether moieties and (2) urea, thiourea, amide,thioamide, dithiobiuret, and/or biuret moieties and to urethane/ureaprepolymers and polymers thereof. These modified polyamines are usefulas starting materials for the fabrication of urea/urethane polymers suchas foams, elastomers, plastics, coatings and adhesives, and are alsouseful in the fabrication of epoxy resins.

In general it is known to prepare polyurethanes containing urea moietiesby the reaction of a polyol and water with an isocyanate and a chainextender as disclosed in Sweeney, Reaction Injection Molding Machineryand Processes (1987). Many other types of polymers and oligomerscontaining urea moieties in their backbone are known materials which canbe prepared in a variety of ways. The majority of such materials areprepared by the reaction of an isocyanate with an amine. The resultingproducts can range from simple monomers as disclosed in U.S. Pat. Nos.3,294,749, 3,386,955, and 3,386,956, to oligomers as disclosed in U.S.Pat. Nos. 3,248,424 and 4,332,953, to soluble polymers as disclosed inU.S. Pat. No. 3,639,338, to dispersions in polyols as disclosed inGerman Patent 3,125,402. It is generally known that the introduction ofurea moieties into a polyurea/urethane polymer improves the hightemperature mechanical properties of the polymer.

Compounds or polymers containing trifunctional biuret moieties aregenerally produced by the reaction of a polyisocyanate with water. Insuch a reaction, a small number of isocyanate moieties are hydrolyzed toamino moieties by reaction with water. These amino moieties, in thepresence of larger quantities of isocyanate moieties, react to formpolyisocyanates containing urea moieties. Further reaction of the ureamoieties with additional polyisocyanates produces polyisocyanatescontaining biuret moieties. These biuret-containing isocyanates havebeen known for many years and have been used in a variety ofapplications, for example as shown in U.S. Pat. Nos. 4,028,313:4,203,875: 4,284,544: 4,289,813: 4,305,977: 4,388,245: and 4,449,591. Itis generally recognized that the inclusion of trifunctional biuretmoieties into a polyurea/urethane polymer produces a material havingincreased cross-link density.

Polyamides of polycarboxylic acids and poly(alkyleneoxy)polyamines arewell-known compositions. Polyurethane coating compositions based on thereaction products of poly(propyleneoxy)polyamines with isocyanate-polyolprepolymers blocked with lactams are disclosed in Jpn 59/226062 (1984).Polyether polyols containing amide groups produced from partiallyaminated polyether polyols and adipoyl chloride or terephthaloylchloride by reactions with isocyanates to produce urethane polymers aredisclosed in DE 2,559,372 (1977).

It is also known to prepare isocyanate-functional prepolymers havingurea moieties or biuret moieties or combinations thereof. Suchisocyanate-functional prepolymers are prepared by first reacting apolyhydroxyl compound such as a polyether polyol with excess isocyanate.The resulting isocyanate-functional prepolymer is then chain-extendedwith reactions with polyamine or amino alcohols to produce polymerscontaining urethane and urea moieties in their backbones, such as shownin U.S. Pat. Nos. 3,471,449: 3,583,937: 3,627,714: 3,668,173 and3,936,409. In some instances, the polymers contain only urea moieties intheir backbones. In other cases, the polymers contain both urea andbiuret moieties in their backbones. It is also known to react anisocyanate-functional prepolymer with a monofunctional amine to givepolymers or oligomers which contain urea moieties near the end of themolecule as shown in U.S. Pat. No. 4,522,986.

In the polyurethanes and polyureas of the prior art containing ureaand/or biuret moieties, the urea and/or biuret moieties are found toreside only in the hard segment of the resulting polyurethane orpolyurea. Such polyureas/urethanes are observed to exhibit propertiessuch as modulus, strength, hardness, toughness and solvent resistancewhich are less than are desired for many applications.

In view of such deficiencies of such prior art materials, it would behighly desirable to provide a polyurethane or polyurea having thedesirable properties contributed by having urea, thiourea, dithiobiuretand/or biuret moieties without sacrificing significantly the propertiesof modulus, strength, hardness, toughness and solvent resistance.

SUMMARY OF THE INVENTION

In one aspect, this invention is a modified polyamine comprising abackbone portion containing at least one polyalkyleneoxy moiety and oneor more internal biuret, thiourea, dithiobiuret, or thioamide moieties,and a plurality of primary amino groups wherein each amino group isseparated from each biuret, thiourea, dithiobiuret, or thioamide moietyby at least one alkylene, cycloalkylene, aralkylene, arylene, oralkyleneoxy moiety with 4-20 carbon atoms, or at least onepolyalkyleneoxy moiety containing from 2-50 alkyleneoxy units.

In a second aspect, this invention is a modified polyamine with amolecular weight of at least 2000 comprising a backbone portioncontaining at least one polyalkyleneoxy moiety and two or more internalurea moieties, and a plurality of primary amino groups wherein eachamino group is separated from each urea moiety by at least one alkylene,cycloalkylene, aralklene, arylene, or alkyleneoxy moiety with 4-20carbon atoms, or at least one polyalkyleneoxy moiety containing from2-50 alkyleneoxy units.

In a third aspect, this invention is a modified polyamine comprising abackbone portion containing at least one polyalkyleneoxy moiety and atleast two amino-carbonyl moieties different from each other which twomoieties are selected from the group consisting of urea, biuret,thiourea, dithiobiuret, thioamide and amide wherein each amino group isseparated from each amino-carbonyl moiety by at least one alkylene,cycloalkylene, aralkylene, arylene, or alkyleneoxy moiety with 4-20carbon atoms, or at least one polyalkyleneoxy moiety with 2-50alkyleneoxy units.

In a fourth aspect, this invention is an isocyanate-functionalprepolymer comprising the reaction product of one or more modifiedpolyamines with a backbone portion containing at least onepolyalkyleneoxy moiety and one or more moieties selected from the groupconsisting of urea, biuret, thiourea, dithiobiuret, thioamide, and amidewith at least one organic polyisocyanate such that the reaction producthas terminal isocyanate moieties.

In a fifth aspect, this invention is a polymer formed by the reaction ofthe aforementioned isocyanate-functional prepolymer with at least oneactive hydrogen-containing compound.

In a sixth aspect, this invention is a urethane/urea polymer formed bythe reaction of one or more modified polyamines with a backbone portioncontaining at least one polyalkyleneoxy moiety and one or more moietiesselected from the group consisting of urea, biuret, thiourea,dithiobiuret, thioamide, and amide with at least one organicpolyisocyanate. In this sixth aspect, it is optional and often preferredto employ, in addition to the aforementioned modified polyamine, one ormore other active hydrogen-containing compounds in the reaction to formthe urethane/urea polymer.

In a seventh aspect, this invention is a post-cured urethane/ureapolymer which has physical properties substantially better than those ofthe polymer prior to the post-cure.

The resulting urethane/urea polymers of this invention have superiorproperties such as higher modulus, greater strength, increased hardnessand toughness and superior solvent resistance when compared to similarpolymers which do not contain either urea, biuret, thiourea,dithiobiuret, thioamide, or amide moieties, and polyalkyleneoxymoieties. The increased modulus observed for the polymers of thisinvention prepared from aliphatic polyamines enable the manufacture ofplastic parts having superior stiffness at lower hard segment contentswhich results in less cost than conventional polyurethane/urea polymers.The polymers of this invention also exhibit superior green strength ondemold when fabricated in reaction injection molding equipment. Thissuperior green strength allows the use of lower mold temperatures whichresults in economic and handling advantages. In many cases, theurethane/urea polymers of this invention cure faster than conventionalurethane/urea polymers. This results in the economic advantage ofreduced cure schedules.

In addition, the modified polyamines of the invention may be contactedwith a cyclic lactone under reaction conditions sufficient to form anactive hydrogen-containing compound with at least one hydroxyl endgroup. Preferably, this cyclic lactone is caprolactone or butyrolactone.These active hydrogen-containing compounds comprise a backbone portioncontaining at least one polyalkyleneoxy moiety and one or more internalurea, biuret, thiourea, dithiobiuret, or thioamide moieties, and aplurality of primary amino end groups and at least one hydroxyl endgroup, wherein each amino or hydroxyl end group is separated from eachurea, biuret, thiourea, dithiobiuret, or thioamide moiety by at leastone alkylene, cycloalkylene, aralkylene, arylene, or alkyleneoxy moietywith 4-20 carbon atoms, or at least one polyalkyleneoxy moietycontaining from 2-50 alkyleneoxy units. These active hydrogen-containingcompounds which contain at least one hydroxyl end group may be contactedwith isocyanates under reaction conditions sufficient to formprepolymers or polymers, optionally in the presence of additional activehydrogen-containing compounds.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

When the modified polyamines of the present invention are diamines, theyare generally represented by the formula:

    NH.sub.2 --R--[X--R].sub.n --NH.sub.2                      I

wherein each R is independently in each occurrence an alkylene,cycloalkylene, aralkylene, aryl, alkyleneoxy, or polyalkyleneoxy moiety,wherein at least one R is polyalkyleneoxy; X is independently in eachoccurrence an acyclic moiety selected from the group consisting of urea,biuret, thiourea, dithiobiuret, amide, and thioamide; when a urea moietyX is ##STR1## when a biuret moiety X is ##STR2## when a thiourea moietyX is ##STR3## when a dithiobiuret moiety X is ##STR4## when an amidemoiety X is ##STR5## where R' is alkylene, cycloalkylene, aralkylene,arylene, and when a thioamide moiety X is ##STR6## and n is an integerbetween 1 and 50, and preferably between 2 and 50. Correspondingstructures can be used when the modified polyamines are triamines andhigher polyamines.

The modified polyamines of the invention are prepared by contacting apolyalkyleneoxy polyamine with urea, thiourea, biuret, dithiobiuret, apolycarboxylic acid, or a polythiocarboxylic acid, or a combinationthereof, optionally in the presence of a C₄₋₂₀ alkylene-,cycloalkylene-, aralkylene-, or arylene polyamine.

The polyalkyleneoxy polyamines used in preparing the modified polyaminesof the invention are well-known compositions which are conventionallyprepared by the reductive amination of polyether polyols using hydrogenand ammonia in the presence of catalyst. This reductive amination ofpolyols is described in U.S. Pat. Nos. 3,128,311; 3,152,998; 3,236,895;3,347,926; 3,654,370; 4,014,933 and 4,153,581, the relevant portions ofwhich are hereby incorporated by reference.

Polyalkyleneoxy polyamines having 3-aminopropoxy end groups are alsowell-known compositions which can be used in preparing the modifiedpolyamines of this invention. Such polyamines can be obtained by thecyanoethylation of polyamines with acrylonitrile followed byhydrogenation to the corresponding polyamines . The synthesis ofmaterials of this type is described in Rylander, Catalytic Hydrogenationin Organic Synthesis (1979) and in U.S. Pat. Nos. 3,471,563; 3,880,928;3,880,929; 3,896,174, the relevant portions of which are herebyincorporated by reference.

Optionally, other polyamines can be used in addition to thepolyalkyleneoxy polyamines. These polyamines can be aliphatic,cycloaliphatic, aromatic, alkylene aromatic, araliphatic, orheterocyclic. Preferably, the amino moieties in such polyamines aresufficiently spaced apart to prevent the formation of cyclic ureamoieties if the polyamine is reacted with urea. Preferably, thepolyamine has a molecular weight of at least about 60, more preferablyat least about 70, and most preferably at least about 80; and ispreferably no greater than about 3000, more preferably no greater thanabout 2000, and most preferably no greater than about 1500.

Specific examples of suitable additional polyamines includebutylenediamine, pentylenediamine, 2-methyl-1,5-pentanediamine,hexamethylenediamine, dodecamethylenediamine, trimethyldiaminohexane,2,2'-bisaminopropylmethylamine, diethylenetriamine,triethylenetetraamine, and tetraethylenepentamine, dipropylenetriamine,piperazine, N,N'-bis-aminoethylpiperazine, triazine, 4-aminobenzylamine,4-aminophenylethylamine, 1,4-diaminocyclohexane, phenylenediamines,naphthylenediamines, condensates of aniline and formaldehyde such asmethylenediphenylamine, toluenediamine, bisaminomethyl benzenes and thederivatives of the above-mentioned aromatic amines includingbutylenediamine, hexamethylenediamine, dodecamethylenediamine,methylenediphenylamine, and toluenediamine. Especially preferred arebutylenediamine, hexamethylenediamine, methylenediphenylamine andtoluenediamine. If C₄₋₁₂ aliphatic amines are used, they may containminor quantities of C₂₋₃ amines, but these are preferably absent as theymay form cyclic urea moieties when reacted with urea.

The modified polyamines of this invention which contain internal biuretor thiobiuret moieties in their backbones can be prepared from thereaction of biuret or dithiobiuret with a polyamine. Biuret is an itemof commerce having the formula: ##STR7## Dithiobiuret is a well-knowncompound having the formula: ##STR8## It can be made, for example, bythe action of hydrogen sulfide on NH₂ C(=NH)NHCN (as disclosed in U.S.Pat. No. 2,371,112 and French Patent 2,004,212).

In the preparation of the modified polyamines containing one or morebiuret or dithiobiuret moieties in their backbones, one or morepolyalkyleneoxy polyamines are contacted with biuret or dithiobiuret,optionally in the presence of C₄₋₂₀ alkylene, cycloalkylene, aralkylene,or arylene polyamines, depending on which product is desired, underconditions sufficient to produce a corresponding biuret- ordithiobiuret-modified polyamine. Preferably, such reactions are carriedout at temperatures in the range from about 100° C. to 200° C., morepreferably from 110° C. to 175° C. and most preferably from 125° C. toabout 160° C. The time of the reaction, while dependent upon thetemperature used, is preferably in the range from 1 to 48 hours, mostpreferably from about 2 to 8 hours when the reaction temperature isabout 150° C. and from about 5 to 24 hours when the reaction temperatureis about 125° C.

Several types of modified polyamines useful in making the prepolymersand polymers of the invention which contain a limited amount of ureamoieties but no thiourea, biuret, dithiobiuret, amide or thioamidemoieties in their backbones are known compositions which can be preparedby a variety of techniques. For example, in one method, a polyetherpolyamine as described hereinbefore can be reacted with urea under theconditions described in U.S. Pat. Nos. 4,002,598; 4,115,360; 4,116,938;and 4,178,427. Alternatively, such polyamines containing a limitedamount of urea moieties in their backbones are prepared by the reactionof the polyamine polyethers with diphenyl carbonate with thecorresponding removal of phenol under conditions as described in U.S.Pat. Nos. 4,002,598; 4,115,360; and 4,178,427. The foregoing referencesalso describe a third process for preparing such polyamines containing alimited amount of urea moieties by reacting a polyether polyamine withphosgene. Of the foregoing techniques, it is generally desirable toemploy the reaction of the polyether polyamine with urea to provide thedesired urea-containing polyamine. However, these urea polyamines of theprior art, which have an average of less than two internal urea moietiesper molecule and low molecular weight, have been found to offersubstantially less improvement in the physical properties ofpolyurethanes and polyureas prepared from them.

The modified polyamines of this invention which contain urea moietiesbut no biuret, dithiobiuret, thiourea, amide, or thioamide moieties intheir backbones are characterized by having at least two internal ureamoieties per molecule and a molecular weight of at least 2000.Preferably these modified polyamines contain three or more internal ureamoieties per molecule. It is most preferred that these modifiedpolyamines contain four or more internal urea moieties per molecule. Themolecular weight of these modified polyamines is at least about 2000,more preferably at least about 3000; and is preferably no greater thanabout 100,000, more preferably no greater than about 50,000, and mostpreferably no greater than about 20,000.

Several types of modified polyamines useful in making the prepolymersand polymers of the invention which contain amide moieties but no urea,thiourea, biuret or dithiobiuret moieties in their backbones are knowncompositions which can be prepared by a variety of techniques. Forexample, in one method, an excess of a polyether polyamine as describedhereinbefore can be reacted with polyacids under conditions whereby theacid moieties on the polyacid react with the amino moieties in thepolyether polyamine to form amide linkages and the excess amino moietiesin the polyether polyamine represent amino end groups. Examples of thisprocess can be found in Jpn 51/125429, Jpn 51/75737, and U.S. Pat. No.4,082,708. In another process for making polyether polyamines with amidemoieties in their backbone, esters of polycarboxylic acids and/oranhydrides can be used in place of, or in addition to, thepolycarboxylic acids used above. Examples can be found in DE 2,552,455;DE 2,552,518; DE 2,814,566: and U.S. Pat. Nos. 4,128,525 and 4,119,615.Epoxy resins can be included, such as in U.S. Pat. No. 4,133,803.Caprolactam can be included in the reactions of polyether polyamineswith polyacids as taught in DE 3,006,961. Acid chlorides can be used inplace of acids such as in DE 2,559,372. The relevant portions ofreferences identified in this paragraph are incorporated by reference.

The modified polyamines of this invention which contain internalthioamide moieties in their backbone can be prepared from the reactionof an excess of a polyamine as described hereinbefore with polythioacidsunder conditions whereby the acid moieties of the polythioacid reactwith the amino moieties in the polyether polyamine to form thioamidelinkages and the excess amino moieties in the polyether polyamine remainas amino end groups. Thioacid chlorides or thioesters can be used inplace of thioacids to produce the internal thioamide moieties.

The modified polyamines of this invention which contain internalthiourea moieties in their backbones can be prepared from the reactionof thiourea with polyalkyleneoxy polyamines, optionally in the presenceof C₄₋₂₀ alkylene, cycloalkylene, aralkylene, arylene, or alkyleneoxypolyamines. Thiourea is an item of commerce having the formula: ##STR9##

In the preparation of these novel modified polyamines containing one ormore thiourea moieties in their backbones, one or more of theabove-named polyamines are contacted with thiourea under conditionssufficient to produce the desired product. Preferably, such reactionsare carried out at temperatures in the range from about 100° C. to 200°C., more preferably from 125° C. to 200° C. and most preferably from150° C. to 175° C. The time of the reaction, while dependent upon thetemperature used, is preferably in the range from about 3 to 48 hours,most preferably from 12 to 24 hours when the reaction temperature isabout 175° C.

Modified polyamines containing at least two different moieties selectedfrom the group consisting of urea, biuret, thiourea, dithiobiuret,thioamide, and amide are also novel modified polyamines of thisinvention. Some of these modified polyamines can be prepared by thereaction of a polyether polyamine with a mixture of biuret and ureaunder the conditions described hereinabove. Alternatively, such modifiedpolyamines containing both urea and biuret moieties can be prepared byfirst reacting a polyether polyamine with urea to form a modifiedpolyamine containing urea moieties in its backbone and then reactingthat product with biuret to form a modified polyamine containing bothurea and biuret moieties in its backbone. Either the reaction with ureaor biuret can be carried out first. This stepwise process is preferredsince the optimum conditions for each reaction are slightly different.

A modified polyamine containing thiourea moieties and one or more of thefollowing moieties: urea, biuret, dithiobiuret, amide, or thioamide, canbe prepared by first reacting a polyether polyamine with thiourea toform a modified polyamine containing thiourea moieties in its backboneand then reacting that product with one or more of the following: urea,biuret, dithiobiuret, a polycarboxylic acid, or a polythiocarboxylicacid, depending on which combination of moieties is desired. Conversely,modified polyamines containing one or more of the following moieties:urea, biuret, dithiobiuret, amide, or thioamide, can be reacted withthiourea to form products containing thiourea moieties and one or moreof the following moieties: urea, biuret, dithiobiuret, amide, orthioamide. Alternatively, such modified polyamines can be prepared byreacting a polyether polyamine with a mixture of thiourea and one ormore of the following: urea, biuret, polycarboxylic acid, dithiobiuret,or polythiocarboxylic acid.

A modified polyamine containing amide moieties can be first preparedfrom a polyether polyamine and a polycarboxylic acid (or by otherprocesses described hereinbefore) followed by reaction with one or moreof the following: urea, biuret, thiourea, dithiobiuret, orpolythiocarboxylic acid, to produce a product containing both amidemoieties and one or more of the following moieties: urea, biuret,thiourea, dithiobiuret, or thioamide, in its backbone, depending onwhich product is desired. Conversely, modified polyamines containing oneor more of the following moieties: urea, biuret, thiourea, dithiobiuret,or thioamide, can be reacted with polyacids to form the correspondingproduct containing amide moieties in its backbone.

A modified polyamine containing dithiobiuret moieties and one or more ofthe following moieties: urea, thiourea, biuret, amide, or thioamide, canbe prepared by reacting a polyether polyamine with dithiobiuret and oneor more of the following: urea, thiourea, biuret, polycarboxylic acid,or polythiocarboxylic acid, depending on which product is desired.Either the reaction with the dithiobiuret or one or more of theaminocarbonyls or aminothiocarbonyls can be carried out first. Thisstepwise process is preferred since the optimum conditions for eachreaction are slightly different.

A modified polyamine containing thioamide moieties and one or more ofthe following moieties: urea, thiourea, biuret, dithiobiuret, or amide,can be prepared by reacting a polyether polyamine withpolythiocarboxylic acid and one or more of the following: urea,thiourea, biuret, dithiobiuret, or polycarboxylic acid, depending whichproduct is desired. Either the reaction with the polythiocarboxylic acidor one or more of the aminocarbonyls or aminothiocarbonyls may becarried out first. This step wise process is preferred since the optimumconditions for each reaction are slightly different.

The stoichiometry of the reactants used to prepare the modifiedpolyamines containing urea, thiourea, biuret and/or dithiobiuretmoieties can vary depending upon the number of internal urea, thiourea,biuret and/or dithiobiuret moieties desired in the average backbonemolecule. For example, in the case of the reaction of a diamine with abiuret, a molar ratio of two diamines per one biuret will give a productwhich contains about one biuret moiety per average polyamine molecule.In contrast, a diamine biuret mole ratio of 1.3:1 will give a modifiedpolyamine product which contains about four biuret moieties per averagemolecule. In the case of urea-containing polyamines, a molar ratio oftwo diamine units to one urea unit will give a modified polyamineproduct which contains about 1 urea moiety per average product molecule.A diamine:urea ratio of 1.3:1 will give a product which contains about 4urea moieties per average polyamine molecule.

Although it is possible to prepare modified polyamines containing urea,thiourea, biuret and/or dithiobiuret moieties in their backbones insolvents, it is generally preferred to prepare them in a neat condition.However, when solvents are used, they are generally inert organicsolvents which are more volatile than the resulting product. Examples ofsuch solvents include alcohols, ethers, amides, sulfoxides, and certainhydrocarbons such as aniosole, phenyl ethyl ether, cumene, hexanol,dodecanol, dimethyl acetamide and dimethyl sulfoxide. Following thereaction, the solvents can be vaporized. Reduced pressures can be usedto increase reaction rate by facilitated ammonia removal. This techniquecan be applied toward the final stages of reaction to increaseconversion.

For the preparation of any of the aforementioned modified polyamines, itis generally unnecessary to purify the product to any significantdegree. Usually small amounts of unreacted biuret can be removed byfiltration if necessary. If a solvent is employed it can be removed byfractional distillation. Residual ammonia can be removed by heatingunder reduced pressure. When an amide or thioamide is made by thereaction of a polyether polyamine with a polycarboxylic acid orpolythiocarboxylic acid, water is the by-product of the reaction. It ispreferred to include a small amount of solvent in the reaction mixturewhich can remove the water by azeotropic distillation. Toluene, xyleneand cumene are convenient solvents They can be removed by fractionaldistillation after the reaction is complete. Alternatively, the reactioncan be run neat under reduced pressure whereby the water is volatilizedfrom the reaction mixture as it is formed.

In the aforementioned modified polyamines, the end group functionalityof the product is controlled by the functionality of the polyetherpolyamine employed. If a difunctional modified polyamine is desired, apolyether diamine is used to synthesize the product. If higherfunctionality is desired, then a blend of a polyether diamine and apolyether polyamine with a functionality of three or higher can be used.For even higher functionality, only polyethylene polyamines withfunctionalities of three or higher can be employed. When amide and/orthioamide moieties are employed, functionality of the polyacid and/orpolythioacid also controls the functionally of the product.

The particular polyether polyamine selected to prepare the modifiedpolyamine-containing urea, biuret, thiourea, dithiobiuret, thioamide,amide, or mixture thereof is dependent upon the required properties ofthe final product. For example, a polyethyleneoxy polyamine will be usedto add hydrophilic characteristics to the product whereas polymers ofhigher alkyleneoxy polyamines such as polypropyleneoxy, polybutyleneoxyand the like, will be employed to add hydrophobic character to theresultant product. It is understood that even greater hydrophobiccharacteristics can be imparted by the use of higher alkyl-containingmaterials such as epoxides of 1-octene, 1-decene, 1-dodecene,1-hexadecene, and 1-octadecene. Also suitable as starting materials forpreparing polyether polyamines are glycidyl ethers of alcohols such ashexanol, octanol, decanol, dodecanol, tetradecanol, hexadecanol andoctadecanol.

The properties of the resulting urethane polymers can be significantlymodified by the selection of the polyether moieties of the polyamines.For example, polyethyleneoxy moieties are useful when the polyurethanesrequire antistatic properties. Polypropyleneoxy and higher alkyleneoxypolymers are useful in polymers requiring resistance to hydrolysis.Combinations of ethylenexoy and higher alkyleneoxy polymers aredesirable in instances wherein a balance of properties are required.

The modified polyamines of the invention range from viscous liquids tolow melting solids depending upon the molecular weight of the polyamineand the composition of the polyether polyamines used in theirpreparation. Preferably, the number average molecular weight of suchmodified polyamines containing one or more of the following moieties:urea, biuret, thiourea, dithiobiuret, thioamide, or amide, is within therange from about 400 to 100,000 or more, most preferably from about 600to about 40,000. Preferably, the number average molecular weight of suchmodified polyamines containing two or more urea moieties is within therange from about 2,000 to 10,000, most preferably from about 3,000 toabout 20,000.

The amino-functional products containing one or more of the followinginternal moieties: urea, biuret, thiourea, dithiobiuret, thioamide, oramide, have a controllable spacing between these moieties. The molecularweight and molecular weight distribution of the polyether polyaminestarting material will carry over into the modified polyamine productand thereby determine the spacing of the urea, biuret, thiourea, anddithiobiuret moieties. The spacing between amide or thioamide moietiesdepends on the length of the polyacids from which they are prepared. Forexample, if a polyether diamine of 400 molecular weight is used as thereactant, then the modified polyamine product will have approximately a400 molecular weight polyether spacing between each internal urea and/orbiuret moiety. If a polyether diamine of approximately 400 molecularweight is used as reactant with adipic acid, then the modified polyamineproduct will have approximately a 400 molecular weight spacing and a 56molecular weight spacing alternating between successive amide groups.

The amino end groups of the polyamines containing at least on acyclicmoiety selected from the group consisting of urea, thiourea, biuret,dithiobiuret, amide, and thioamide can be converted to the correspondinghydroxyl functional material by reaction with cyclic lactones. As themolar ratio of cyclic lactone:polyamine is increased, a series ofproducts can be produced. At lower molar ratios, activehydrogen-containing compounds which contain both amino and hydroxyl endgroups can be produced. A second class of products which may be producedat higher molar ratios contains only hydroxyl end groups. A third classof products may be produced at even higher molar ratios in whichhydroxyl end groups react further with cyclic lactones to form esterlinkages and a higher molecular weight hydroxyl functional product.

Preferred cyclic lactones are caprolactone and butyrolactone, The mostpreferred reaction temperature is about 180° C. for caprolactone andabout 125° C. for butyrolactone. The conversion of primary amino endgroups to hydroxyl end groups is a way of controlling end groupactivity. The lower reactivity of hydroxyl end groups towardpolyisocyanates allows for the use of these materials in applicationssuch as cast elastomers and flexible foams, where lower reaction ratesare required.

The isocyanate-functional prepolymer compositions of this invention areformed by the reaction of the modified polyamine containing one or moreof the following moieties: biuret, urea, thiourea, dithiobiuret,thioamide, or amide, with excess polyisocyanate.

The polyisocyanates suitable for making the novel compositions of thisinvention include aliphatic, cycloaliphatic, araliphatic, aromatic andheterocyclic polyisocyanates. Specific examples include ethylenediisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylenediisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate,cyclohexane-1,3- and 1,4-diisocyanate and mixtures of these isomers1-isocyanato-3,3,5-trimethyl-5-isocyanato methyl cyclohexane (see e.g.,German Auslegeschrift No. 1,202,785); 2,4- and 2,6-hexahydrotolylenediisocyanate and mixtures of these isomers, hexahydro-1,3- and/or1,4-phenylene diisocyanate, perhydro-2,5'- and/or 4,4'-diphenyl methanediisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylenediisocyanate and mixtures of these isomers, diphenyl methane-2,4'-and/or 4,4'-diisocyanate, naphthylene-1,5-diisocyanate, triphenylmethane-4,4',4"-triisocyanate, polyphenyl polymethylene polyisocyanatesof the type obtained by condensing aniline with formaldehyde, followedby phosgenation and such as described for example in British Patents874,430 and 848,671, perchlorinated aryl polyisocyanates of the typedescribed in German Auslegeschrift 1,157,601, polyisocyanates containingcarbodiimide groups of the type described in German Patent 1,092,007,diisocyanates of the type described in U.S. Pat. No. 3,492,330,polyisocyanates containing allophanate groups of the type described, forexample, in British Patent 994,890, in Belgian Patent 761,626 and inpublished Dutch Patent Application No. 7,102,524, polyisocyanatescontaining isocyanurate groups of the type described in German Patents1,022,789; 1,222,067 and 1,027,394 and in German Offenlegungsschrift1,929,034 and 2,004,048, polyisocyanates containing urethane groups ofthe type described, for example, in Belgian Patent 752,261 or in U.S.Pat. No. 3,394,164, polyisocyanates containing acrylated urea groups asdescribed in German Patent 1,230,778, polyisocyanates containing biuretgroups of the type described, for example, in German Patent 1,101,392,in British Patent 889,050 and in French Patent 7,017,514,polyisocyanates obtained by telomerization reactions of the typedescribed, for example, in Belgian Patent 723,640, polyisocyanatescontaining ester groups of the type described, for example, in BritishPatents 965,474 and 1,072,956, in U.S. Pat. No. 3,567,763 and in GermanPatent 1,231,688 and reaction products of the aforementioned isocyanateswith acetals as described in German Patent 1,072,385.

In addition, derivatives of 4,4'-diphenylmethane diisocyanate which areliquid at room temperature such as, for example, polyisocyanates whichhave carbodiimide groups in their backbone or mixtures thereof may alsobe used. The preparation of these materials is disclosed in U.S. Pat.No. 3,152,162, which is hereby incorporated by reference in itsentirety. An example of a commercial material of this type is Isonate™143L Isocyanate, a product of The Dow Chemical Company.

It is also possible to use the distillation residues containingisocyanate groups accumulating in the commercial production ofisocyanates, optionally in solution in one or more of the aforementionedpolyisocyanates. In addition, it is possible to use mixtures of theaforementioned polyisocyanates

Additional polyisocyanates suitable for use in this invention includethose described by W. Siefken in Justus Liebigs Annalen der Chemie, 562,pp. 75-136, and in U.S. Pat. Nos. 3,284,479; 4,089,835; 4,093,569;4,221,876; 4,310,448; 4,359,550 and 4,495,309.

One class of particularly useful polyisocyanates are the aromaticpolyisocyanates such as 2,4- and 2,6-tolylene diisocyanates and mixturesof these isomers ("TDI"), polyphenyl-polymethylene polyisocyanates ofthe type obtained by condensing aniline with formaldehyde, followed byphosgenation ("crude MDI") and, polyisocyanates containing carbodiimidegroups, urethane groups, allophanate groups, isocyanurate groups, ureagroups or biuret groups ("modified polyisocyanates")

A preferred class of aromatic polyisocyanates is methylenebis(4-phenylisocyanate) or MDI. Pure MDI, quasi- and prepolymers of MDI,modified pure MDI, etc. Materials of this type may be used to preparesuitable RIM elastomers. Since pure MDI is a solid and, thus, ofteninconvenient to use, liquid products based on MDI are often used and areincluded in the scope of the terms MDI or methylenebis(4-phenylisocyanate) used herein. U.S. Pat. No. 3,394,164 is anexample of a liquid MDI product. More generally uretonimine-modifiedpure MDI is included also. This product is made by heating puredistilled MDI in the presence of a catalyst.

In the preparation of such prepolymers, excess isocyanate can be addedto the modified polyamine or the modified polyamine can be added toexcess isocyanate. Preferably, the modified polyamine is added to excessisocyanate under conditions which are well-known for the reaction ofpolyisocyanates with prior art active hydrogen-containing compounds.Examples of such conditions are described in U.S. Pat. Nos. 4,108,842;4,125,522 and 4,476,292, the relevant portions of which are herebyincorporated by reference.

The viscosity of the modified polyamine increases with increasing numberof urea, thiourea, biuret, dithiobiuret, thioamide and/or amide moietiesin the polyamine backbone and with increasing molecular weight of thepolyamine. This increased viscosity in the modified polyamine results inincreased viscosity in the corresponding isocyanate functionalprepolymer. This requires corresponding increases in the reactiontemperature during prepolymer formation. Temperatures of 80° C. to 110°C. or even higher are required as the modified polyamine and/orprepolymer viscosity increases. At the higher temperatures, prepolymerstability is sometimes reduced and chain extension of the prepolymer tothe corresponding polymer needs to be carried out more quickly. Thepresence of mildly acidic prepolymer stabilizers, such as benzoylchloride, can be useful. In some cases an inert solvent, such asdimethylsulfoxide, dimethylformamide or dimethylacetamide, is used toreduce the viscosity of the modified polyamine and the correspondingprepolymer. A chain extender can be added to the prepolymer solution andthe resultant polymer separated. When the polymer is soluble it can becast as a film from solution or it can be precipitated by the additionof a poor solvent or it can be obtained by removal of the solvent.

It is further understood that such prepolymers of this invention mayalso be prepared by the reaction of the modified polyamine and an activehydrogen-containing compound as a mixture with excess polyisocyanate.This is another way to reduce the viscosity of the prepolymer andthereby facilitate its handling. In such prepolymers, the modifiedpolyamine:active hydrogen-containing compound mole ratio is in the rangefrom about 20:1 to about 0.05:1, most preferably from about 10:1 toabout 0.1:1. These mixed amine active hydrogen-containing compoundprepolymers are also isocyanate-functional and are prepared usingconditions known in the prior art as cited hereinbefore.

In a fifth aspect, this invention is a novel urethane and/or ureapolymer formed by the reactions of the aforementionedisocyanate-functional prepolymer of this invention with an activehydrogen-containing compound or mixtures of active hydrogen-containingcompounds. An active hydrogen-containing compound is a compound having aplurality of active hydrogen moieties that are reactive with theZerewitinoff reagent according to a test described by Kohler in 49 Jour.of the Amer. Chem. Soc. 3181 (1927). Examples of such moieties includemercaptan, hydroxyl, primary and secondary amine, and acid groups. Suchcompounds are also referred to as "polyahls". Many such activehydrogen-containing compounds of a lower molecular weight are commonlycalled chain-extenders when used with isocyanate-functional prepolymersand are optionally employed with catalysts and a variety of otheradditives. High molecular weight active hydrogen-containing compoundscan also be used.

The chain-extenders useful to make the compositions of this inventionare preferably difunctional. Mixtures of difunctional and trifunctionalchain-extenders are also useful in this invention. The chain-extendersuseful in this invention include diols, amino alcohols, diamines ormixtures thereof. Low molecular weight linear diols such as1,4-butanediol and ethylene glycol have been found suitable for use inthis invention. Other chain-extenders including cyclic diols such as1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; aromaticring-containing diols such as bishydroxyethylhydroquinone; amide- orester-containing diols or amino alcohols are useful. Aromatic diaminesand aliphatic diamines are suitable chain-extenders. Examples includeethylenediamines, 1-(2-aminoisopropyl-4-methyl-4-aminocyclohexane),1,2-propanediamine, 1,4-butanediamine: 1,6-hexanediamine,diethyltoluenediamine and 1,4-bis-(aminomethyl)cyclohexane. Additionalexamples of useful chain-extenders can be found in U.S. Pat. Nos.4,297,444; 4,202,957; 4,476,292; 4,495,309 and 4,218,543.

Catalysts such as tertiary amines or an organic tin compound or otherpolyurethane catalysts may be used. The organic tin compound maysuitably be a stannous or stannic compound, such as stannous salt of acarboxylic acid, a trialkyltin oxide, a dialkyltin dihalide, adialkyltin oxide, etc., wherein the organic groups of the organicportion of the tin compound are hydrocarbon groups containing from 1 to18 carbon atoms. For example, dibutyltin dilaurate, dibutyltindiacetate, diethyltin diacetate, dihexyltin diacetate,di-2-ethylhexyltin oxide, dioctyltin dioxide, stannous octoate, stannousoleate, etc., or a mixture thereof, may be used. Other catalysts includeorgano zinc, mercury and lead compounds. For some polymers, a catalystis not needed.

Tertiary amine catalysts include trialkylamines (e.g., trimethylamine,triethylamine), heterocyclic amines, such as N-alkylmorpholines (e.g.,N-methylmorpholine, N-ethylmorpholine, dimethyldiaminodiethyl ether,etc.), 1,4-dimethylpiperazine, triethylenediamine, etc., and aliphaticpolyamines, such as N,N,N',N'-tetramethyl-1,3-butanediamine.

Optional additives include anti-foaming agents such as glycerine, anethyl acrylate-2-ethylhexyl acrylate copolymer, dimethyl siloxanecopolymers and silicones; antioxidants such as esters ofβ-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monohydric orpolyhydric alcohols, for example, methanol, octadecanol, 1,6-hexanediol,neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethyleneglycol, pentaerythritol, tris-hydroxyethyl isocyanurate, anddihydroxyethyl oxalic acid diamine; UV absorbers and light stabilizerssuch as 2-(2'-hydroxyphenyl)benzotriazoles and sterically hinderedamines such as bis-(2,2,6,6-tetramethylpiperidyl-sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl)-sebacate,n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonic acid,bis-(2,2,6,6-pentamethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylene diamine and4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine,tris(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarbonicacid and 1,1'-(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone);plasticizers such as phthalates, adipates, glutarates, epoxidizedvegetable oils, and the like: fungicides; pigments; dyes; reactive dyes;moisture scavengers; and the like. In addition, fillers and reinforcingmaterials such as chopped or milled glass fibers, chopped or milledcarbon fibers and/or other mineral fibers are useful.

Approximately stoichiometric amounts of the isocyanate moieties of theisocyanate-functional prepolymers of this invention and the activehydrogen moieties on the active hydrogen-containing compounds are used.The equivalent ratio of isocyanate moieties to total active hydrogenmoieties is between about 0.95:1.00 to 1.00:1.05, more preferred is anisocyanate:active hydrogen-containing compound equivalent ratio of from0.97:1.00 to 1.00:1.03, most preferred is a ratio of 1.00:1.00 to1.00:1.03.

In a sixth aspect, this invention is a novel urethane/urea polymerformed by the reaction of the modified polyamine with a polyisocyanateas defined hereinbefore. Such urethane/urea polymers are optionallyprepared in the presence of other active hydrogen-containing compoundsas defined hereinbefore and catalysts and other additives usedconventionally to prepare urethane and urea polymers. For some polymersa catalyst is not needed.

Approximately stoichiometric amounts of the isocyanate moieties of thepolyisocyanates and the total active hydrogen moieties on the modifiedpolyamine and other active hydrogen-containing compounds, if employed,are used. The equivalent ratio of isocyanate moieties to total activehydrogen moieties is between about 0.90:1.00 to 1.00:1.25: morepreferred is an isocyanate:active hydrogen equivalent ratio of from0.95:1.00 to 1.00:1.15, most preferred is a ratio of 0.98:1.00 to1.00:1.05. The preparation of urethane/urea polymers is well-known inthe art. Examples of typical reaction conditions employed can be foundin U.S. Pat. Nos. 4,460,715 and 4,394,491, the relevant portions ofwhich are hereby incorporated by reference.

The urethane/urea and/or biuret and/or thiourea and/or dithiobiuretand/or thioamide and/or amide polymers of the present invention can befabricated by any fabrication technique known in the art. Usefulprocesses include hand casting (see, for example, U.S. Pat. No.4,476,292) and reaction injection molding (see, for example, U.S. Pat.Nos. 4,297,444 and 4,495,309).

Reaction injection molding (RIM) is a preferred fabrication technique.The relatively high viscosities of the modified polyamines are readilyreduced by heating. This is easily accomplished in RIM equipment byheating the tank and lines. Viscosity is also reduced by blending withchain-extending agents and, optionally, with other activehydrogen-containing compounds. The urethane/urea polymers of thisinvention are useful in automotive body panel applications or automotivefacsia.

In the seventh aspect, this invention is a urethane/urea polymer whichhas been post-cured by heating the urethane/urea polymer that forms thesixth or seventh aspect of this invention to a temperature in the rangefrom about 175° C. to about 200° C. for a period from about 1 to about12 hours or more. To prevent degradation, it is preferred to carry outthe post-curing process in an inert atmosphere, such as nitrogen, whenusing higher temperatures or longer heating periods. As a result of thispost-cure, the properties such as modulus and tensile strength of theresultant polymer are noticeably improved.

Illustrative Embodiments

The following examples are given to illustrate the invention and shouldnot be interpreted as limiting it in any way. Unless stated otherwise,all parts and percentages are given by weight.

Example 1

1A(1). Preparation of a Diamine Containing About Four Urea Moieties perAverage Backbone Molecule; Molecular Weight=9,866.

A diamine containing about 4 urea moieties per average backbone moleculeis prepared by reacting Jeffamine™ D-2000 (2332.2 g, 1.10 moles; anaminated poly(propylene glycol) of 2036 number average molecular weight,a product of the Jefferson Chemical Division of Texaco) with urea (154.8g, 0.91 mole; D-2000 : urea molar ratio=1.20) in a 3-liter, 3-neckedflask equipped with a thermometer, overhead stirrer, condenser,temperature control system and maintained under a nitrogen atmosphere.The contents of the flask are heated at 150° C. for 16 hours. Theammonia formed during the reaction is directed into an aqueous scrubber.The reactor is then cooled to ambient temperature and treated on arotary evaporator at 90° C. under a 20 mm Hg vacuum for 3 hours. Theproduct is a light yellow, viscous liquid with the following properties:basicity, 0.202 meq/g; molecular weight by end group titration, 866;Brookfield viscosity, 13,820 cps; Tg, -64° C. Carbon-13 NMR indicatedthe presence of internal urea moieties (157.8 ppm) and amino end groups.

1A(2). Preparation of a Diamine Containing About Nine Urea Moieties perAverage Backbone Molecule; Molecular Weight=20,700.

A diamine containing about 9 urea moieties per average backbone moleculeis prepared by reacting Jeffamine™ D-2000 (396.98 g, 0.1944 mole) withurea (11.12 g, 0.185 mole: D-2000:urea molar ratio=1.05) in the samereactor setup used in Example 1A(1), except using a 500-ml reactor. Thecontents of the flask are heated at 175° C. for 23 hours. The ammoniaformed during the reaction is directed into an aqueous scrubber. Thereactor is then cooled to ambient temperature and treated on a rotaryevaporator at 90° C. under a 20 mm Hg vacuum for 3 hours. The product isa light yellow, viscous liquid with the following properties: basicity,0.0966 meq/g; molecular weight by end group titration, 20,700;Brookfield viscosity, 141,200 cps.

1A(3). Preparation of a Diamine Containing About Twenty Urea Moietiesper Average Backbone Molecule: Molecular Weight=42,800.

A diamine containing about 20 urea moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-2000 (364.37 g, 0.1784mole) with urea (10.51 g, 0.1749 mole; D-2000:urea molar ratio=1.02) inthe same reactor setup used in Example 1A(2). The contents of the flaskare heated at 175° C. for 23 hours. The ammonia formed during thereaction is directed into an aqueous scrubber. The reactor is thencooled to ambient temperature and treated on a rotary evaporator at 90°C. under a 20 mm Hg vacuum for 3 hours. The product is a light yellow,viscous liquid with the following properties: basicity, 0.0467 meq/g;molecular weight by end group titration, 42,800; Brookfield viscosity,627,000 cps.

1A(4). Preparation of a Diamine Containing About Three Urea Moieties perAverage Backbone Molecule: Molecular Weight=8023.

A diamine containing about 3 urea moieties per average backbone moleculeis prepared by reacting an aminated poly(butylene glycol) of 2070 numberaverage molecular weight (348.08 g, 0.168 mole) with urea (8.41 g, 0.140mole; aminated B-2000:urea molar ratio=1.20) in the same reaction setupused in Example 1A(2). The contents of the flask are heated at 150° C.for 24 hours. The ammonia formed during the reaction is directed into anaqueous scrubber. The reactor is then cooled to ambient temperature andtreated on a rotary evaporator at 90° C. under a 20 mm Hg vacuum for 3hours. The product is a light yellow, viscous liquid with the followingproperties: basicity, 0.244 meq/g; molecular weight by end grouptitration, 8203; Brookfield viscosity, 11,500 cps. This example showsthat polyamines containing polyoxybutylene moieties in their backbonescan be used to make the compositions of this invention.

1A(5). Preparation of a Diamine Containing About Seven Urea Moieties perAverage Backbone Molecular; Molecular Weight=15,307.

A diamine containing about 7 urea moieties per average backbone moleculeis prepared by reacting an aminated poly(butylene glycol) of 2070 numberaverage molecular weight (350.23 g, 0.169 mole) with urea (9.96 g, 0.166mole; aminated B-2000:urea molar ratio=1.02) in the same reaction setupused in Example 1A(2). The contents of the flask are heated at 175° C.for 50 hours. The ammonia formed during the reaction is directed into anaqueous scrubber. The reactor is then cooled to ambient temperature andtreated on a rotary evaporator at 90° C. under a 20 mm Hg vacuum for 3hours. The product is a light yellow, viscous liquid with the followingproperties: basicity, 0.1307 meq/g; molecular weight by end grouptitration, 15,307; Brookfield viscosity, 63,600 cps. This example showsthat polyamines containing polyoxybutylene moieties in their backbonescan be used to make the compositions of this invention.

1A(6). Preparation of a Diamine Containing About Three Urea Moieties perAverage Backbone Molecule Based on D-400/D-2000 Blends; MolecularWeight=3367.

A diamine containing about 3 urea moieties per average backbone moleculeis prepared by reacting a blend of Jeffamine™ D-400 (1592.5 g, 3.488moles) and Jeffamine™ D-2000 (1736.5 g, 0.872 mole) with urea (209.5 g,3.488 moles) in the same reactor setup used in Example 1A(1), exceptusing a 5-liter reactor. The contents of the flask are heated at 175° C.for 20 hours. The ammonia formed during the reaction is directed into anaqueous scrubber. The reactor is then cooled to ambient temperature andtreated on a rotary evaporator at 90° C. under a 20 mm Hg vacuum for 3hours. The product is a light yellow, viscous liquid with the followingproperties: basicity, 0.594 meq/g; molecular weight by end grouptitration, 3367; 3.35 urea moieties/average molecule by perchloric acidtitration; Brookfield viscosity, 19,000 cps at 25° C.

1A(7). Preparation of a Diamine Containing About Three Urea Moieties perAverage Backbone Molecule Based on D-400/D-2000 Blends; MolecularWeight=4710.

A diamine containing about 3 urea moieties per average backbone moleculeis prepared by reacting a blend of Jeffamine™ D-400 (815.4 g, 1.786mole) and Jeffamine™ D-2000 (2374.7 g, 1.191 moles) with urea (143.0 g,2.381 moles) in the same reactor setup used in Example 1A(6). Thecontents of the flask are heated at 175° C. for 24 hours. The ammoniaformed during the reaction is directed into an aqueous scrubber. Thereactor is then cooled to ambient temperature and treated on a rotaryevaporator at 90° C. under a 20 mm Hg vacuum for 3 hours. The product isa light yellow, viscous liquid with the following properties: basicity,0.425 meq/g; molecular weight by end group titration, 4710; 3.36 ureamoieties/average molecule by perchloric acid titration; Brookfieldviscosity, 11,760 cps at 25° C.

1A(8). Preparation of a Diamine Containing About Four Urea Moieties perAverage Backbone Molecule Based on D-400/D-2000 Blends; MolecularWeight=6326.

A diamine containing about 4 urea moieties per average backbone moleculeis prepared by reacting a blend of Jeffamine™ D-400 (433.7 g, 0.950mole) and Jeffamine™ D-2000 (2841.7 g, 1.425 moles) with urea (114.1 g,1.900 moles) in the same reactor setup used in Example 1A(6). Thecontents of the flask are heated at 175° C. for 24 hours. The ammoniaformed during the reaction is directed into an aqueous scrubber. Thereactor is then cooled to ambient temperature and treated on a rotaryevaporator at 90° C. under a 20 mm Hg vacuum for 3 hours. The product isa light yellow, viscous liquid with the following properties: basicity,0.316 meq/g; molecular weight by end group titration, 6326; 3.75 ureamoieties/average molecule by perchloric acid titration; Brookfieldviscosity, 15,200 cps at 24° C.

1A(9). Preparation of a Diamine Containing About Four Urea Moieties perAverage Backbone Molecule Based on D-2000; Molecular Weight=11,119.

A diamine containing about 4 urea moieties per average backbone moleculeis prepared by reacting Jeffamine™ D-2000 (3375.8 g, 1.653 moles) withurea (82.7 g, 1.378 moles) in the same reactor setup used in Example1A(6). The contents of the flask are heated at 150° C. for 39 hours. Theammonia formed during the reaction is directed into an aqueous scrubber.The reactor is then cooled to ambient temperature and treated on arotary evaporator at 90° C. under a 20 mm Hg vacuum for 3 hours. Theproduct is a light yellow, viscous liquid with the following properties:basicity, 0.180 meq/g; molecular weight by end group titration, 11,119;4.40 urea moieties/average molecule by perchloric acid titration;Brookfield viscosity, 24,050 cps at 23° C.

1A(10). Preparation of a Diamine Containing About Six Urea Moieties perAverage Backbone Molecule Based on D-400; Molecular Weight=3443.

A diamine containing about 6 urea moieties per average backbone moleculeis prepared by reacting Jeffamine™ D-400 (3080.8 g, 6.839 moles) withurea (357.2 g, 5.947 moles) in the same reactor setup used in Example1A(6). The contents of the flask are heated at 150° C. for 23 hours. Theammonia formed during the reaction is directed into an aqueous scrubber.The reactor is then cooled to ambient temperature and treated on arotary evaporator at 90° C. under a 20 mm Hg vacuum for 3 hours. Theproduct is a light yellow, viscous liquid with the following properties:basicity, 0.581 meq/g; molecular weight by end group titration, 3443;6.36 urea moieties/average molecule by perchloric acid titration;Brookfield viscosity, 341,000 cps at 25° C.

1A(11). Preparation of a Diamine Containing About Sixteen Urea Moietiesper Average Backbone Molecule Based on D-2000; Molecular Weight=33,471.

A diamine containing about 16 urea moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-2000 (3206.1 g, 1.570moles) with urea (92.5 g, 1.539 moles) in the same reactor setup used inExample 1A(6). The contents of the flask are heated at 150° C. for 94hours. The ammonia formed during the reaction is directed into anaqueous scrubber. The reactor is then cooled to ambient temperature andtreated on a rotary evaporator at 90° C. under a 20 mm Hg vacuum for 3hours The product is a light yellow, viscous liquid with the followingproperties: basicity, 0.0598 meq/g; molecular weight by end grouptitration, 33,471; 15.65 urea moieties/average molecule by perchloricacid titration; Brookfield viscosity, 228,800 cps at 25° C.

1A(12). Preparation of a Diamine Containing Four Urea Moieties perAverage Backbone Molecule; Molecular Weight=1912.

Jeffamine™ D-400 (3775.7 g, 8.64 moles) and urea (432.0 g, 7.20 moles),at a D-400:urea molar ratio =1.20 are combined in the same reactor setupused in Example 1A(6). The contents of the flask are heated at 135° C.for 24 hours during which time ammonia is evolved and passed into anaqueous scrubber. The resultant viscous liquid is treated on a rotaryevaporator at 90° C under a 20 mm Hg vacuum to remove all of the ammoniaby-product. The product is a clear, light yellow, viscous liquid havingan amine content of 1.046 meq/g which corresponds to a molecular weightof 1912 by end group analysis; Brookfield viscosity, 41,100 cps. ¹³ Cnuclear magnetic resonance analysis shows internal urea carbonylmoieties (158.0 ppm), the methylene carbon attached to urea(--CH(CH₃)NHC(0)NH--, 45.7 ppm) and the methylene carbon attached to theamino end groups (--CH(CH₃)NH₂, 46.8 ppm).

1A(13). Preparation of an Isocyanate-Functional Prepolymer Based on aUrea Backbone Diamine and MDI.

The diamine containing about 4 urea moieties per average molecule ofExample 1A(12) (76.20 g) is placed in a 100-ml resin pot equipped withthermometer, overhead stirrer, temperature controlled at 80° C. by anoil bath and maintained under a nitrogen atmosphere. One drop (about 15mg) of benzoyl chloride is added as a prepolymer stabilizer. Thecontents of the reactor are equilibrated at 80° C. and the benzoylchloride dissolved by thorough agitation. Freshly distilled4,4'-methylenedi(phenyl-isocyanate) (MDI, 44.70 g, Isonate™ 125 M,manufactured by The Dow Chemical Company), is added by syringe to thereactor under nitrogen cover. The contents of the reactor are stirred at80° C. for one hour.

The prepolymer is then analyzed for isocyanate content (ASTM D-1638-74).A sample (1.818 g) is dissolved in dry dimethyl formamide (25 ml) andtreated with an excess of a standard di-n-butylamine solution in drytoluene (0.2 N, 50 ml) for 15 minutes at ambient temperature withstirring. Additional dry dimethyl formamide (25 ml) is added and theexcess amine is titrated using 0.1 N HCl. The weight percent isocyanateis found to be 10.15.

1A(14). Preparation of a Urethane/Urea Polymer From anIsocyanate-Functional Prepolymer.

The isocyanate-functional prepolymer of Example 1A(13) (105.92 g) isthoroughly degassed under vacuum and quickly poured into a 150-mlplastic cup. Two drops (about 30 mg) of a catalyst solution are added(10.0 weight percent dibutyltin dilaurate in poly(propylene glycol) of2000 molecular weight) 1,4-Butanediol (11.3 g, distilled from CaH₂)which had been thoroughly degassed under vacuum is added quickly to givea 1.05 index (molar ratio of isocyanate:hydroxyl=1.05). The mixture isstirred rapidly for 32 seconds and then poured into a preheated mold(6.0"×6.0"×0.125"). The sample is then cured at 121° C. (250° F.) forone hour. A urethane/urea plastic plaque is obtained upon demolding.

1A(15). Preparation of an Isocyanate-Functional Prepolymer Based on aUrea Backbone Diamine and TDI.

The diamine containing about 4 urea moieties per average molecule ofExample 1A(12) (78.20 g) is placed in the same reaction setup used inExample 1A(13). One drop (about 15 mg) of benzoyl chloride is added as aprepolymer stabilizer. The contents of the reactor are equilibrated at80° C. and the benzoyl chloride dissolved by thorough agitation Toluenediisocyanate (TDI; 80 percent 2,4-isomer and 20 percent 2,6-isomer;38.71 g), is added by syringe to the reactor under nitrogen cover. Thecontents of the reactor are stirred at 80° C. for one hour.

The prepolymer is then analyzed for isocyanate content (ASTM D-1638-74).A sample (1.938 g) is dissolved in dry dimethyl formamide (25 ml) andtreated with an excess of a standard di-n-butylamine solution in drytoluene (0.2 N, 50 ml) for 15 minutes at ambient temperature withstirring. Additional dry dimethyl formamide (25 ml) is added and theexcess amine is titrated using 0.1 N HCl. The weight percent isocyanateis found to be 11.20.

1A(16). Preparation of a Urethane/Urea Polymer From anIsocyanate-Functional Prepolymer.

The isocyanate-functional prepolymer of Example 1A(15) (104.62 g) isthoroughly degassed under vacuum and quickly poured into a 150-mlplastic cup. Two drops (about 30 mg) of a catalyst solution are added(10.0 weight percent dibutyltin dilaurate in poly(propylene glycol) of2000 molecular weight). 1,4-Butanediol (12.6 g, distilled from CaH₂)which had been thoroughly degassed under vacuum is added quickly to givea 1.05 index (molar ratio of isocyanate:hydroxyl=1.05). The mixture isstirred rapidly for 34 seconds and then poured into a preheated mold(6.0"×6.0"×0.125"). The sample is then cured at 121° C. (250° C.) forone hour. A urethane/urea plastic plaque is obtained upon demolding.

1B. Preparation of a Diamine Containing One Urea Moiety per AverageBackbone Molecule; Molecular Weight=2562.

A diamine containing about one urea moiety per average backbone moleculeis prepared by reacting an aminated poly(propylene glycol) with a numberaverage molecular weight of 1207 (2704.8 g, 2.16 moles) with urea (64.8g, 1.08 moles) in the same reactor setup used in Example 1A(6). Theammonia formed during the reaction is directed into an aqueous scrubber.The reactor is heated at 150° C. for 18 hours, cooled to ambienttemperature and treated on a rotary evaporator at 90° C. under 20 mm Hgvacuum for 3 hours. The product is a light yellow, viscous liquid withthe following properties: basicity, 0.781 meq/g: molecular weight by endgroup titration, 2562; Brookfield viscosity, 1,138 cps. ¹³ C nuclearmagnetic resonance indicates the presence of internal urea carbonylmoieties (157.8 ppm), the methylene carbon is attached to urea(--CH(CH₃)NHC(0)NH--, 45.7 ppm), and the methylene carbon attached tothe amino end groups (--CH(CH₃)NH₂, 46.8 ppm).

1C. Preparation of a Diamine Containing About One Urea Moiety perAverage Backbone Molecule; Molecular Weight=4120.

A diamine containing about one urea moiety per average backbone moleculeis prepared by reacting Jeffamine™ D-2000 (4024.6 g, 1.89 moles) withurea (56.78 g, 0.95 mole) in the same reactor setup used in Example1A(6). The ammonia formed during the reaction is directed into anaqueous scrubber. The reactor is heated at 150° C. for 16 hours, cooledto ambient temperature and treated on a rotary evaporator at 90° C.under a 20 mm Hg vacuum for 3 hours. The product is a light yellow,viscous liquid with the following properties: basicity, 0.485 meq/g;molecular weight by end group titration, 4120; Brookfield viscosity,1,840 cps. ¹³ C nuclear magnetic resonance indicates the presence ofinternal urea moieties (157.8 ppm) and amino end groups.

1D. Preparation of a Diamine Containing Two Amide Moieties per AverageBackbone Molecule; Molecular Weight=920.

A diamine containing 2 amide moieties per average backbone molecule isprepared by reacting Jeffamine™ D-400 (1716.0 g, 4.00 moles) with adipicacid (292.0 g, 2.00 moles) in a 3-liter reactor equipped with anoverhead stirrer, thermometer, condenser, a Dean Stark trap, atemperature controller and maintained under a nitrogen cover. Thereactor is heated to 125° C. to dissolve the reactants by forming thecorresponding amine salt. Toluene (150 ml) is added and the reactor isheated at 152° C. to 162° C. for 10 hours while separating thewater-toluene azeotropically boiling mixture. The reactor is then heatedat 162° C. to 170° C. and 2 mm Hg vacuum for 4 hours to remove thetoluene and any residual water. The product is a light yellow, viscousliquid with the following properties: basicity, 2.176 meq/g; molecularweight by end group titration, 920; Brookfield viscosity, 3,250 cps. ¹³C nuclear magnetic resonance indicates the presence of internal amidemoieties (172.1 ppm).

1E. Preparation of a Diamine Based on Jeffamine™ D-400 and Adipic Acid;Molecular Weight=2004.

A diamine containing about 6 amide moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-400 (2094.0 g, 4.93 moles)with adipic acid (554.1 g, 3.79 moles) in the same equipment used inExample 1D. The reactor is heated to 125° C. to dissolve the reactantsby forming the corresponding amine salt. Toluene (150 ml) is added andthe reactor is heated at 150° C. to 171° C. for 16 hours whileseparating the water-toluene azeotropically boiling mixture. The reactoris then heated at 162° C. to 170° C. and 2 mm Hg vacuum for 4 hours toremove the toluene and any residual water. The product is a lightyellow, viscous liquid with the following properties: basicity, 0.998meq/g; molecular weight by end group titration, 2004; Brookfieldviscosity, 113,800 cps at 25° C.; Tg -37° C. ¹³ C nuclear magneticresonance indicates the presence of internal amide moieties (172.1 ppm).

1F. Preparation of a Diamine Based on Jeffamine™ D-230 and Adipic Acid;Molecular Weight=1889.

A diamine containing about 10 amide moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-230 (2203.6 g, 9.163moles; an aminated poly(propylene glycol) with a number averagemolecular weight of about 230, manufactured by the Jefferson ChemicalDivision of Texaco) with adipic acid (1115.9 g, 7.636 moles) in the sameequipment used in Example 1D, except using a 5-liter reactor. Thereactor is heated to 125° C. to dissolve the reactants by forming thecorresponding amine salt. Toluene (225 ml) is added and the reactor isheated at 150° C. to 170° C. for 16 hours while separating thewater-toluene azeotropically boiling mixture. The reactor is then heatedat 162° C. to 170° C. and 2 mm Hg vacuum for 4 hours to remove thetoluene and any residual water. The product is a light yellow, veryviscous glass with the following properties: basicity, 1.059 meq/g;molecular weight by end group titration, 1889; Brookfieldviscosity, >2,000,000 cps at 25° C. ¹³ C nuclear magnetic resonanceindicates the presence of internal amide moieties (172.1 ppm).

1G. Preparation of a Diamine Based on Jeffamine™ D-2000 and Adipic Acid;Molecular Weight=9542.

A diamine containing about 6 amide moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-2000 (3500.0 g, 1.719moles) with adipic acid (193.5 g, 1.322 moles) in the same equipmentused in Example 1F. The reactor is heated to 125° C. to dissolve thereactants by forming the corresponding amine salt. Toluene (225 ml) isadded and the reactor is heated at 150° C. to 170° C. for 16 hours whileseparating the water-toluene azeotropically boiling mixture. The reactoris then heated at 162° C. to 170° C. and 2 mm Hg vacuum for 4 hours toremove the toluene and any residual water. The product is a lightyellow, viscous liquid with the following properties: basicity, 0.2096meq/g; molecular weight by end group titration, 9542; Brookfieldviscosity, 26,300 cps at 25° C. ¹³ C nuclear magnetic resonanceindicates the presence of internal amide moieties (172.1 ppm).

1H. Preparation of a Diamine Based on Jeffamine™ D-400 and Adipic Acid;Molecular Weight=3133.

A diamine containing about 9.5 amide moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-400 (544.80 g, 1.20 moles)with adipic acid (146.14 g, 1.00 mole) in the same equipment used inExample 1D except the flask was 1-liter. The reactor is heated to 140°C. to dissolve the reactants by forming the corresponding amine salt.Toluene (50 ml) is added and the reactor is heated at 157° C. to 161° C.for 20 hours while separating the water-toluene azeotropically boilingmixture. The reactor is then heated to 190° C. and the bulk of thetoluene removed. The crude product is then heated at 100° C. under a15-mm Hg vacuum for 5 hours to remove residual toluene. The product is alight yellow, viscous liquid with a basicity of 0.638 meq/g whichcorresponds to a molecular weight of 3133. The number of amide moietiesper average molecule is calculated to be about 9.5.

1I. Preparation of a Diamine Based on Jeffamine™ D-400 and Adipic Acid;Molecular Weight=5259.

A diamine containing about 17.1 amide moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-400 (499.40 g, 1.10 moles)with adipic acid (146.14 g, 1.00 mole) in the same equipment used inExample 1H. The reactor is heated to 140° C. to dissolve the reactantsby forming the corresponding amine salt. Toluene (50 ml) is added andthe reactor is heated at 157° C. to 160° C. for 22 hours whileseparating the water-toluene azeotropically boiling mixture. The reactoris then heated to 190° C. and the bulk of the toluene removed. The crudeproduct is then heated at 100° C. under a 15-mm Hg vacuum for 5 hours toremove residual toluene. The product is a light yellow, viscous liquidwith a basicity of 0.380 meq/g which corresponds to a molecular weightof 5259. The number of amide moieties per average molecule is calculatedto be about 17.1.

1J. Preparation of a Diamine Based on Jeffamine™ D-400 and Adipic Acid;Molecular Weight=10,413.

A diamine containing about 35.3 amide moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-400 (476.70 g, 1.05 moles)with adipic acid (146.14 g, 1.00 mole) in the same equipment used inExample 1H. The reactor is heated to 140° C. to dissolve the reactantsby forming the corresponding amine salt. Toluene (50 ml) is added andthe reactor is heated at 157° C. to 166° C. for 65 hours whileseparating the water-toluene azeotropically boiling mixture. The reactoris then heated to 190° C. and the bulk of the toluene removed. The crudeproduct is then heated at 100° C. under a 15-mm Hg vacuum for 5 hours toremove residual toluene. The product is a light yellow, viscous liquidwith a basicity of 0.192 meq/g which corresponds to a molecular weightof 10,413. The number of amide moieties per average molecule iscalculated to be about 35.3.

1K. Preparation of a Diamine Containing About Six Amide Moieties perAverage Backbone Molecule Based on D-400/D-2000 Blends: MolecularWeight=4828.

A diamine containing about 8 amide moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-400 (1372.6 g, 3.006moles) and Jeffamine™ D-2000 (1499.1 g; 0.7515 mole) with adipic acid(439.3 g, 3.006 moles) in the same equipment used in Example 1F. Thereactor is heated to 140° C. to dissolve the reactants by forming thecorresponding amine salt. Toluene (150 ml) is added and the reactor isheated at 157° C. to 166° C. for 48 hours while separating thewater-toluene azeotropically boiling mixture. The reactor is then heatedto 190° C. and the bulk of the toluene removed. The crude product isthen heated at 100° C. under a 15-mm Hg vacuum for 5 hours to removeresidual toluene. The product is a light yellow, viscous liquid with abasicity of 0.414 meq/g which corresponds to a molecular weight of 4828.

1L. Preparation of a Diamine Containing About Six Amide Moieties perAverage Backbone Molecule Based on D-400/D-2000 Blends; MolecularWeight=5565.

A diamine containing about 8 amide moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-400 (984.4 g, 2.155 moles)and Jeffamine™ D-2000 (2897.6 g; 1.437 moles) with adipic acid (420.1 g,2.875 moles) in the same equipment used in Example 1F. The reactor isheated to 140° C. to dissolve the reactants by forming the correspondingamine salt. Toluene (150 ml) is added and the reactor is heated at 157°C. to 164° C. for 48 hours while separating the water-tolueneazeotropically boiling mixture. The reactor is then heated to 190° C.and the bulk of the toluene removed. The crude product is then heated at100° C. under a 15-mm Hg vacuum for 5 hours to remove residual toluene.The product is a light yellow, viscous liquid with a basicity of 0.359meq/g which corresponds to a molecular weight of 5565.

1M. Preparation of a Diamine Containing About Six Amide Moieties perAverage Backbone Molecule Based on D-400/D-2000 Blends; MolecularWeight=7282.

A diamine containing about 8 amide moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-400 (421.2 g, 0.9225 mole)and Jeffamine™ D-2000 (2760.1 g; 1.384 moles) with adipic acid (269.61g, 1.845 moles) in the same equipment used in Example 1F. The reactor isheated to 140° C. to dissolve the reactants by forming the correspondingamine salt. Toluene (150 ml) is added and the reactor is heated at 157°C. to 164° C. for 48 hours while separating the water-tolueneazeotropically boiling mixture. The reactor is then heated to 190° C.and the bulk of the toluene removed. The crude product is then heated at100° C. under a 15-mm Hg vacuum for 5 hours to remove residual toluene.The product is a light yellow, viscous liquid with a basicity of 0.275meq/g which corresponds to a molecular weight of 7282.

1N. Preparation of a Diamine Containing About Five Amide Moieties perAverage Backbone Molecule Based on Sebacic Acid; Molecular Weight=7909.

A diamine containing about 5 amide moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-2000 (3220.7 g; 1.588moles) with sebacic acid (240.9 g, 1.191 moles) in the same equipmentused in Example 1F. The reactor is heated to 140° C. to dissolve thereactants by forming the corresponding amine salt. Toluene (150 ml) isadded and the reactor is heated at 155° C. to 164° C. for 48 hours whileseparating the water-toluene azeotropically boiling mixture. The reactoris then heated to 190° C. and the bulk of the toluene removed. The crudeproduct is then heated at 100° C. under a 15-mm Hg vacuum for 5 hours toremove residual toluene. The product is a light yellow, viscous liquidwith a basicity of 0.252 meq/g which corresponds to a molecular weightof 7909.

10. Preparation of a Diamine Containing About Eight Amide Moieties perAverage Backbone Molecule Based on Sebacic Acid; Molecular Weight=2604.

A diamine containing about 8 amide moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-400 (2518 4 g; 5.902moles) with sebacic acid (895.3 g, 4.427 moles) in the same equipmentused in Example 1F. The reactor is heated to 140° C. to dissolve thereactants by forming the corresponding amine salt. Toluene (150 ml) isadded and the reactor is heated at 155° C. to 164° C. for 48 hours whileseparating the water-toluene azeotropically boiling mixture. The reactoris then heated to 190° C. and the bulk of the toluene removed. The crudeproduct is then heated at 100° C. under a 15-mm Hg vacuum for 5 hours toremove residual toluene. The product is a light yellow, viscous liquidwith a basicity of 0.768 meq/g which corresponds to a molecular weightof 2604.

1P. Preparation of a Diamine Containing About Eight Amide Moieties perAverage Backbone Molecule Based on Adipic Acid; Molecular Weight=9289.

A diamine containing about 8 amide moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-2000 (3320.8 g; 1.626moles) with adipic acid (182.8 g, 1.251 moles) in the same equipmentused in Example 1F. The reactor is heated to 140° C. to dissolve thereactants by forming the corresponding amine salt. Toluene (150 ml) isadded and the reactor is heated at 155° C. to 164° C. for 48 hours whileseparating the water-toluene azeotropically boiling mixture. The reactoris then heated to 190° C. and the bulk of the toluene removed. The crudeproduct is then heated at 100° C. under a 15-mm Hg vacuum for 5 hours toremove residual toluene. The product is a light yellow, viscous liquidwith a basicity of 0.215 meq/g which corresponds to a molecular weightof 9289.

Example 2

2A. Preparation of a Diamine Containing Four Biuret Moieties per AverageBackbone Molecule; Molecular Weight=2240.

Jeffamine™ D-400 (2121.0 g, 5.00 moles) and biuret (412.3 g, 4.00moles), at a D-400:biuret molar ratio=1.25 are combined in the samereactor setup used in Example 1A(1). The contents of the flask areheated at 150° C. for 8 hours during which time ammonia is evolved andpassed into an aqueous scrubber. The resultant slurry is treated on arotary evaporator at 90° C. under a 20 mm Hg vacuum to finish thereaction and remove all of the ammonia by-product. The slurry is thenfiltered to a clear, light yellow, viscous liquid product having anamine content of 0.893 meq/g which corresponds to a molecular weight of2240 by end group analysis: Brookfield viscosity, 287,600 cps. ¹³ Cnuclear magnetic resonance analysis shows internal biuret moieties(155.0 ppm) in the backbone and amino end groups.

2B. Preparation of an Isocyanate-Functional Prepolymer Based on a BiuretBackbone Diamine and MDI.

The diamine containing about 4 biuret moieties per average molecule ofExample 2A (75.90 g) is placed in a 100-ml resin pot equipped withthermometer, over-head stirrer, temperature controlled at 80° C. by anoil bath and maintained under a nitrogen atmosphere. One drop (about 15mg) of benzoyl chloride is added as a prepolymer stabilizer. Thecontents of the reactor are equilibrated at 80° C. and the benzoylchloride dissolved by thorough agitation. Freshly distilled4,4'-methylenedi(phenyl-isocyanate) (MDI, 44.20 g, Isonate™ 125M,manufactured by The Dow Chemical Company), is added by syringe to thereactor under nitrogen cover. The contents of the reactor are stirred at80° C. for one hour.

The prepolymer is then analyzed for isocyanate content (ASTM D-1638-74).A sample (1.608 g) is dissolved in dry dimethyl formamide (25 ml) andtreated with an excess of a standard di-n-butylamine solution in drytoluene (0.2 N, 50 ml) for 15 minutes at ambient temperature withstirring. Additional dry dimethyl formamide (25 ml) is added and theexcess amine is titrated using 0.1 N HCl. The weight percent isocyanateis found to be 10.25.

2C. Preparation of a Urethane/Urea Polymer From an Isocyanate-FunctionalPrepolymer.

The isocyanate-functional prepolymer of Example 2B (104.80 g) isthoroughly degassed under vacuum and quickly poured into a 150-mlplastic cup. Two drops (about 30 mg) of a catalyst solution are added(10.0 weight percent dibutyltin dilaurate in poly(propylene glycol) of2000 molecular weight). 1,4-Butanediol (11.2 g, distilled from CaH₂)which had been thoroughly degassed under vacuum is added quickly to givea 1.05 index (molar ratio of isocyanate:hydroxyl=1.05). The mixture isstirred rapidly for 28 seconds and then poured into a preheated mold(6.0"×6.0"×0.125"). The sample is then cured at 121° C. (250° F.) forone hour. A urethane/urea plastic plaque is obtained upon demolding.

Example 3

Preparation of a Diamine Containing About Two Biuret Moieties perAverage Backbone Molecule; Molecular Weight=928

A diamine containing about 2 biuret moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-400 (2070.4 g, 4.86 moles)with biuret (250.3 g, 2.43 moles) in the same reactor setup used inExample 1A(1). The ammonia formed during the reaction is directed intoan aqueous scrubber. The reactor is heated at 150° C. for 2.5 hours,cooled to ambient temperature, treated on a rotary evaporator at 90° C.under a 20 mm Hg vacuum for 3 hours and filtered. The product is a lightyellow, viscous liquid with the following properties: basicity, 2.155meq/g; molecular weight by end group titration, 928; Brookfieldviscosity, 2,440 cps. ¹³ C nuclear magnetic resonance indicates thepresence of internal biuret moieties (154.6 ppm) and amino end groups.

Example 4

Preparation of a Diamine Containing Four Biuret Moieties per AverageBackbone Molecule: Molecular; Molecular Weight=2065

A diamine containing about 4 biuret moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-400 (2060.2 g, 4.80 moles)with biuret (370.8 g, 3.60 moles) in the same reactor setup used inExample 1A(1). The ammonia formed during the reaction is directed intoan aqueous scrubber. The reactor is heated at 150° C. for 7.0 hours,cooled to ambient temperature, treated on a rotary evaporator at 90° C.under a 20 mm Hg vacuum for 3 hours and filtered. The product is a lightyellow, viscous liquid with the following properties: basicity, 0.968meq/g; molecular weight by end group titration, 2065; Brookfieldviscosity, 179,400 cps. ¹³ C nuclear magnetic resonance indicates thepresence of internal biuret moieties (154.8 ppm) and amino end groups.

Example 5

Preparation of a Diamine Containing One Biuret Moiety per AverageBackbone Molecule; Molecular Weight=2819

A diamine containing about one biuret moiety per average backbonemolecule is prepared by reacting an aminated poly(propylene glycol) witha number average molecular weight of 1207 (1750.4 g, 1.405 moles) withbiuret (72.38 g, 0.702 mole) in the same reactor setup used in Example1A(1). The ammonia formed during the reaction is directed into anaqueous scrubber. The reactor is heated at 150° C. for 8.0 hours, cooledto ambient temperature, treated on a rotary evaporator at 90° C. under a20 mm Hg vacuum for 3 hours and filtered. The product is a light yellow,viscous liquid with the following properties: basicity, 0.710 meq/g;molecular weight by end group titration, 2819: Brookfield viscosity,2,528 cps. ¹³ C nuclear magnetic resonance indicates the presence ofinternal biuret moieties (154.8 ppm) and amino end groups.

Example 6

Preparation of a Diamine Containing About Four Biuret Moieties perAverage Backbone Molecule; Molecular Weight=11,173

A diamine containing about 4 biuret moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-2000 (3900.7 g, 1.83moles) with biuret (151.2 g, 1.47 moles) in the same reactor setup usedin Example 1A(6). The ammonia formed during the reaction is directedinto an aqueous scrubber. The reactor is heated at 150° C. for 8.0hours, cooled to ambient temperature, treated on a rotary evaporator at90° C. under a 20 mm Hg vacuum for 3 hours and filtered. The product isa light yellow, viscous liquid with the following properties: basicity,0.179 meq/g; molecular weight by end group titration, 11,173; Brookfieldviscosity, 39,000 cps. ¹³ C nuclear magnetic resonance indicates thepresence of internal biuret moieties (154.8 ppm) and amino end groups.

Example 7

Preparation of a Diamine Containing Polyoxybutylene Moieties and FourBiuret Moieties per Average Backbone Molecule; Molecular Weight=10,516

A diamine containing about 4 biuret moieties per average backbonemolecule is prepared by reacting an aminated poly(butylene glycol) witha number average molecular weight of 2070 (329.46 g, 0.1591 mole) withbiuret (13.12 g, 0.1273 mole) in the same reactor setup used in Example1A(2) except using a 500-ml flask. The ammonia formed during thereaction is directed into an aqueous scrubber. The reactor is heated at150° C. for 24 hours, cooled to ambient temperature, treated on a rotaryevaporator at 90° C. under a 20 mm Hg vacuum for 3 hours and filtered.The product is a light yellow, viscous liquid with the followingproperties: basicity, 0.1902 meq/g; molecular weight by end grouptitration, 10,516; Brookfield viscosity, 47,100 cps. This example showsthat polyoxybutylene moieties can be incorporated into polymer backbone

Example 8

8(A) Preparation of a Diamine Containing About Three Thiourea Moietiesper Average Molecule; Molecular Weight=2192.

A diamine containing about 3 thiourea moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-400 (3127.9 g, 6.850moles) with thiourea (434.5 g, 5.709 moles; D-400:thiourea molarratio=1.20:1) in the same reaction setup used in Example 1A(6). Thecontents of the flask are heated at 175° C. for 24 hours. The ammoniaformed during the reaction is directed into an aqueous scrubber. Thereactor is then cooled to ambient temperature and treated batchwise on arotary evaporator at 90° C. under a 20 mm Hg vacuum for 3 hours. Theproduct is a light yellow, viscous liquid with the following properties:basicity, 0.9122 meq/g; molecular weight by end group titration, 2192;3.05 thiourea moieties/molecule by perchloric acid titration; Brookfieldviscosity, 43,500 cps at 25° C. ¹³ C NMR shows the carbonyl carbon at181.4 ppm.

8(B). Preparation of a Diamine Containing About Four Thiourea Moietiesper Average Molecule; Molecular Weight=12,400.

A diamine containing about 4 thiourea moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-2000 (3233.2 g, 1.622moles) with thiourea (102.0 g, 1.351 moles; D-2000:thiourea molar ratio=1.20:1) in the same reaction setup used in Example 1A(6). The contentsof the flask are heated at 175° C. for 24 hours. The ammonia formedduring the reaction is directed into an aqueous scrubber. The reactor isthen cooled to ambient temperature and treated batchwise on a rotaryevaporator at 90° C. under a 20 mm Hg vacuum for 3 hours. The product isa light yellow, viscous liquid with the following properties: basicity,0.161 meq/g; molecular weight by end group titration; Brookfieldviscosity, 29,750 cps at 25° C. ¹³ C NMR shows the carbonyl carbon at181.4 ppm.

8(C). Preparation of a Diamine Containing About Two Thiourea Moietiesper Average Molecule; Molecular Weight=1667.

A diamine containing about 2 thiourea moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-400 (323.8 g, 0.709 mole)with thiourea (41.5 g, 0.546 mole; D-400:thiourea molar ratio=1.30:1) inthe same reaction setup used in Example 1A(2). The contents of the flaskare heated at 150° C. for 71 hours. The ammonia formed during thereaction is directed into an aqueous scrubber. The reactor is thencooled to ambient temperature and treated on a rotary evaporator at 90°C. under a 20 mm Hg vacuum for 3 hours. The product is a light yellow,viscous liquid with the following properties: basicity, 1.200 meq/g;molecular weight by end group titration; Brookfield viscosity, 21,050cps at 25° C. ¹³ C NMR shows the carbonyl carbon at 181.4 ppm.

8(D). Preparation of a Diamine Containing About Two Thiourea Moietiesper Average Molecule; Molecular Weight=1734.

A diamine containing about 2 thiourea moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-400 (456.6 g, 0.693 mole)with thiourea (40.5 g, 0.533 mole; D-400:thiourea molar ratio=1.30:1) inthe same reaction setup used in Example 1A(2). The contents of the flaskare heated at 175° C. for 22 hours. The ammonia formed during thereaction is directed into an aqueous scrubber. The reactor is thencooled to ambient temperature and treated on a rotary evaporator at 90°C. under a 20 mm Hg vacuum for 3 hours. The product is a light yellow,viscous liquid with the following properties: basicity, 1.153 meq/g;molecular weight by end group titration, 1734; 2.50 thioureamoieties/molecule by perchloric acid titration; Brookfield viscosity,23,100 cps at 25° C. ¹³ C NMR shows the carbonyl carbon at 181.4 ppm.

8(E). Preparation of a Diamine Containing About Three Thiourea Moietiesper Average Molecule; Molecular Weight=2051.

A diamine containing about 3 thiourea moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-400 (342 7 g, 0.750 mole)with thiourea (47.6 g, 0.625 mole: D-400:thiourea molar ratio=1.20:1) inthe same reaction setup used in Example 1A(2). The contents of the flaskare heated at 175° C. for 22 hours. The ammonia formed during thereaction is directed into an aqueous scrubber. The reactor is thencooled to ambient temperature and treated on a rotary evaporator at 90°C. under a 20 mm Hg vacuum for 3 hours. The product is a light yellow,viscous liquid with the following properties: basicity, 0.975 meq/g;molecular weight by end group titration, 2051; 3.12 thioureamoieties/molecule by perchloric acid titration; Brookfield viscosity,31,050 cps at 25° C. ¹³ C NMR shows the carbonyl carbon at 181.4 ppm.

8(F). Preparation of a Diamine Containing About Three Thiourea Moietiesper Average Molecule; Molecular Weight=8799.

A diamine containing about 3 thiourea moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-2000 (332.1 g, 0.167 mole;an aminated poly(propylene glycol) of 1995 number average molecularweight, a product of Texaco) with thiourea (10.6 g, 0.139 mole;D-2000:thiourea molar ratio=1.20:1) in the same reaction setup used inExample 1A(2). The contents of the flask are heated at 175° C. for 21hours. The ammonia formed during the reaction is directed into anaqueous scrubber. The reactor is then cooled to ambient temperature andtreated on a rotary evaporator at 90° C. under a 20 mm Hg vacuum for 3hours. The product is a light yellow, viscous liquid with the followingproperties basicity, 0.227 meq/g; molecular weight by end grouptitration, 8799; 3.31 thiourea moieties/molecule by perchloric acidtitration; Brookfield viscosity, 12,540 cps at 25° C. ¹³ C NMR shows thecarbonyl carbon at 181.4 ppm.

8(G). Preparation of a Diamine Containing About One Thiourea Moiety perAverage Molecule; Molecular Weight=898.

A diamine containing about one thiourea moiety per average backbonemolecule is prepared by reacting Jeffamine™ D-400 (1427.5 g, 3.126mole)s with thiourea (119.0 g, 0.563 mole; D-400:thiourea molarratio=2.00:1) in the same reaction setup used in Example 1A(1) exceptthat a 2-liter reactor was used. The contents of the flask are heated at175° C. for 5 hours. The ammonia formed during the reaction is directedinto an aqueous scrubber. The reactor is then cooled to ambienttemperature and treated on a rotary evaporator at 90° C. under a 20 mmHg vacuum for 3 hours. The product is a light yellow, viscous liquidwith the following properties: basicity, 2.227 meq/g; molecular weightby end group titration, 898; 0.93 thiourea moieties/molecule byperchloric acid titration; Brookfield viscosity, 932 cps at 25° C. ¹³ CNMR shows the carbonyl carbon at 181.4 ppm.

8(H). Scaled Up Preparation of a Diamine Containing About Four ThioureaMoieties per Average Molecule; Molecular Weight=2218.

A diamine containing about 4 thiourea moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-400 (3335.9 g, 7.306moles) with thiourea (463.4 g, 6.088 moles; D-400:thiourea molarratio=1.20:1) in the same reaction setup used in Example 1A(6). Thecontents of the flask are heated at 175° C. for 20 hours. The ammoniaformed during the reaction is directed into an aqueous scrubber. Thereactor is then cooled to ambient temperature and treated batchwise on arotary evaporator at 90° C. under a 20 mm Hg vacuum for 3 hours. Theproduct is a light yellow, viscous liquid with the following properties:basicity, 0.902 meq/g; molecular weight by end group titration, 2218;2.97 thiourea moieties/molecule by perchloric acid titration; Brookfieldviscosity, 55,000 cps at 24° C. ¹³ C NMR shows the carbonyl carbon at181.4 ppm.

8(I). Scaled Up Preparation of a Diamine Containing About Four ThioureaMoieties per Average Molecule; Molecular Weight=12,400.

A diamine containing about 4 thiourea moieties per average backbonemolecule is prepared by reacting Jeffamine™ D-2000 (3233.2 g, 1.622moles) with thiourea (102.9 g, 1.351 mole;s D-2000:thiourea molarratio=1.20:1) in the same reaction setup used in Example 1A(6). Thecontents of the flask are heated at 175° C. for 24 hours. The ammoniaformed during the reaction is directed into an aqueous scrubber. Thereactor is then cooled to ambient temperature and treated batchwise on arotary evaporator at 90° C. under a 20 mm Hg vacuum for 3 hours. Theproduct is a light yellow, viscous liquid with the following properties:basicity, 0.161 meq/g; molecular weight by end group titration, 12,400;3.70 thiourea moieties/molecule by perchloric acid titration; Brookfieldviscosity, 29,750 cps at 25° C. ¹³ C NMR shows the carbonyl carbon at181.4 ppm.

Example 9

Preparation of a Diamine Containing About Four Thiourea Moieties perAverage Molecule and a Poly(oxybutylene) Backbone; MolecularWeight=10,905.

A diamine containing about 4 thiourea moieties per average backbonemolecule is prepared by reacting an aminated poly(butylene glycol) of2071 number average molecular weight (328.2 g, 0.159 mole) with thiourea(10.05 g, 0.132 mole; diamine:thiourea molar ratio=1.20:1) in the samereaction setup used in Example 1A(2). The contents of the flask areheated at 175° C. for 22 hours. The ammonia formed during the reactionis directed into an aqueous scrubber. The reactor is then cooled toambient temperature and treated on a rotary evaporator at 90° C. under a20 mm Hg vacuum for 3 hours. The product is a light yellow, viscousliquid with the following properties: basicity, 0.183 meq/g; molecularweight by end group titration, 10,905; 4.11 thiourea moieties/moleculeby perchloric acid titration; Brookfield viscosity, 14,780 cps at 25° C.¹³ C NMR shows the carbonyl carbon at 181.4 ppm.

Example 10

Preparation of a Diamine Containing Two Biuret Moieties and One UreaMoiety per Average Backbone Molecule; Molecular Weight=1890.

A diamine containing 2 biuret moieties per average backbone molecule isfirst prepared by reacting Jeffamine™ D-400 (2070.4 g, 4.86 moles) withbiuret (250.3 g, 2.43 moles) in the same reactor setup used in Example1A(6). The ammonia formed during the reaction is directed into anaqueous scrubber. The reactor is heated at 150° C. for 2.5 hours, cooledto ambient temperature and filtered. The product is a light yellow,viscous liquid with the following properties: basicity, 2.155 meq/g;molecular weight by end group titration, 2440. ¹³ C nuclear magneticresonance indicates the presence of internal biuret moieties (154.6ppm).

The diamine prepared above containing 2 biuret moieties per averagebackbone molecule (2052.1 g, 2.21 moles) and urea (66.34 g, 1.10 moles)are combined in the same reactor used above. The reactor is heated at135° C. for 20 hours. The content of the reactor is then treated on arotary evaporator at 20 mm Hg vacuum to remove residual ammonia. Theproduct is a light yellow, viscous liquid with the following properties:basicity, 1.058 meq/g; molecular weight by end group titration, 1890;Brookfield viscosity, 57,400 cps; Tg -38° C. ¹³ C nuclear magneticresonance indicates the presence of internal biuret moieties (154.6 ppm)and internal urea moieties (158.0).

This example demonstrates the preparation of a diamine containing bothurea and biuret moieties in its backbone.

Example 11

Preparation of a Diamine Containing Four Amide Moieties and One BiuretMoiety per Average Backbone Molecule; Molecular Weight =2046.

A diamine containing 2 amide moieties per average backbone molecule isfirst prepared by reacting Jeffamine™ D-400 (1716.0 g, 4.00 moles) withadipic acid (292.0 g, 2.00 moles) in the same reactor setup used inExample 1D. The reactor is heated to 125° C. to dissolve the reactantsby forming the corresponding amine salt. Toluene (150 ml) is added andthe reactor is heated at 152° C. to 162° C. for 10 hours whileseparating the water-toluene azeotropically boiling mixture The reactoris then heated at 162° C. to 170° C. and 2 mm Hg vacuum for 4 hours toremove the toluene and any residual water. The product is a lightyellow, viscous liquid with the following properties: basicity, 2.176meq/g; molecular weight by end group titration, 3250. ¹³ C nuclearmagnetic resonance indicates the presence of internal amide moieties(172.1 ppm).

The diamine prepared above containing 2 amide moieties per averagebackbone molecule (1809.4 g, 1.967 moles) and biuret (101.32 g, 0.984mole) are combined in the same reactor used in Example 1C. The reactoris heated at 150° C. for 7 hours. The content of the reactor is thentreated on a rotary evaporator at 20 mm Hg vacuum to remove residualammonia. The product is a light yellow, viscous liquid with thefollowing properties: basicity, 0.978 meq/g; molecular weight by endgroup titration, 2046; Brookfield viscosity, 148,800 cps; Tg -36° C. ¹³C nuclear magnetic resonance indicates the presence of both internalbiuret moieties (154.6 ppm) and internal amide moieties (172 5).

This example demonstrates the preparation of a diamine containing bothamide and biuret moieties in its backbone.

Example 12

Preparation of a Diamine Containing Four Amide Moieties and One UreaMoiety per Average Backbone Molecule; Molecular Weight=1956.

A diamine containing 2 amide moieties per average backbone molecule isfirst prepared by reacting Jeffamine™ D-400 (784.8 g, 1.80 moles) withadipic acid (131.53 g, 0.90 mole) in the same reactor setup used inExample 1H. The reactor is heated to 125° C. to dissolve the reactantsby forming the corresponding amine salt. Toluene (150 ml) is added andthe reactor is heated at 152° C. to 162° C. for 10 hours whileseparating the water-toluene azeotropically boiling mixture. The reactoris then heated at 162° C. to 170° C. and 2 mm Hg vacuum for 4 hours toremove the toluene and any residual water. The product is a lightyellow, viscous liquid with the following properties: basicity, 2.161meq/g; molecular weight by end group titration, 925; Brookfieldviscosity, 2950. ¹³ C nuclear magnetic resonance indicates the presenceof internal amide moieties (172.3 ppm).

The diamine prepared above containing 2 amide moieties per averagebackbone molecule (393.83 g, 0.426 mole) and urea (12.75 g, 0.213 mole)are combined in a one-liter flask equipped in the same way as thereactor used in Example 10. The reactor is heated at 150° C. for 17hours. The content of the reactor is then treated on a rotary evaporatorat 20 mm Hg vacuum to remove residual ammonia. The product is a lightyellow, viscous liquid with the following properties: basicity, 1.022meq/g; molecular weight by end group titration, 1956; Brookfieldviscosity, 93,200; Tg -40° C. ¹³ C nuclear magnetic resonance indicatesthe presence of both internal urea moieties (158.0 ppm) and internalamide moieties (172.5 ppm).

This example demonstrates the preparation of a diamine containing bothamide and urea moieties in its backbone.

Example 13

Preparation of a Diamine Containing both Thiourea and Urea Moieties inthe same Molecule; Molecular Weight=1656.

A diamine containing both thiourea moieties and urea moieties in thesame molecule is prepared by reacting a portion of the product fromExample 8(G) (345 1 g, 0.378 mole) with urea (11.34 g, 0.189 mole) inthe same reaction setup used in Example 1A(2). The contents of the flaskare heated at 175° C. for 5 hours. The ammonia formed during thereaction is directed into an aqueous scrubber. The reactor is thencooled to ambient temperature and treated on a rotary evaporator at 90°C. under a 20 mm Hg vacuum for 3 hours. The product is a light yellow,viscous liquid with the following properties: basicity, 1.208 meq/g;molecular weight by end group titration, 1656; 2.56 thiourea plus ureamoieties/molecule by perchloric acid titration; Brookfield viscosity,15,800 cps at 25° C. ¹³ C NMR shows the thiourea carbonyl carbon at181.4 ppm and the urea carbonyl carbon at 157.8 ppm.

Example 14 Preparation of a Diamine Containing both Thiourea and BiuretMoieties in the same Molecule; Molecular Weight=1831.

A diamine containing both thiourea moieties and biuret moieties in thesame molecule is prepared by reacting a portion of the product fromExample 8(G) (356.2 g, 0.390 mole) with biuret (20.09 g, 0.195 mole) inthe same reaction setup used in Example 1A(2). The contents of the flaskare heated at 150° C. for 21 hours. The ammonia formed during thereaction is directed into an aqueous scrubber. The reactor is thencooled to ambient temperature and treated on a rotary evaporator at 90°C. under a 20 mm Hg vacuum for 3 hours. The product is a light yellow,viscous liquid with the following properties: basicity, 1.092 meq/g;molecular weight by end group titration, 1831; 1.92 thioureamoieties/molecule by perchloric acid titration; Brookfield viscosity,35,950 cps at 25° C. ¹³ C NMR shows the thiourea carbonyl carbon at181.4 ppm and the biuret carbonyl carbon at 154.7 ppm.

Example 15

Preparation of a Diamine Containing both Thiourea and Amide Moieties inthe same Molecule; Molecular Weight=2005.

A diamine containing both thiourea moieties and amide moieties in thesame molecule is prepared by reacting a portion of the Example 8(G)(346.2 g, 0.379 mole) with adipic acid (27.68 g, 0.189 mole) in the samereaction setup used in Example 1H. The contents of the flask are heatedat 140° C. for 30 minutes to form the salt intermediate. Toluene (30 ml)was added and the reactor was heated at gentle reflux for 21 hours whilecollecting 6.7 ml of water (theory=6.8 ml) in the trap. The majority ofthe toluene is removed from the trap by increasing the reactortemperature to 185° C. The reactor is then cooled to ambient temperatureand treated on a rotary evaporator at 90° C. under a 10 mm Hg vacuum for5 hours. The product is a light yellow, viscous liquid with thefollowing properties: basicity, 0.998 meq/g; molecular weight by endgroup titration, 2005; Brookfield viscosity, 19,550 cps at 25° C. ¹³ CNMR shows the thiourea carbonyl carbon at 181.4 ppm and the amidecarbonyl carbon at 172.3 ppm.

Example 16

Scaled Up Preparation of a Diamine Containing both Thiourea and AmideMoieties in the Same Molecule: Molecular Weight=1716.

A diamine containing about one thiourea moiety per average backbonemolecule is prepared by reacting Jeffamine™ D-400 (3201.2 g, 6.995moles) with thiourea (266.2 g, 3.498 moles: D-400:thiourea molarratio=2.00:1) in the same reaction setup used in Example 1A(6). Thecontents of the flask are heated at 175° C. for 21 hours. The ammoniaformed during the reaction is directed into an aqueous scrubber. Theproduct is a light yellow, viscous liquid with the following properties:basicity, 2.190 meq/g; molecular weight by end group titration, 913;0.91 thiourea moieties/molecule by perchloric acid titration.

Adipic acid (267.7 g, 1 832 moles) is added to the reactor and a DeanStark trap is added below the condenser. The contents of the flask areheated at 140° C. for 30 minutes to form the salt intermediate. Toluene(250 moles) is added and the reactor is heated at gentle reflux for 48hours while collecting water in the trap. The majority of the toluene isremoved from the trap by increasing the reactor temperature to 185° C.The reactor is then cooled to ambient temperature and treated batchwiseon a rotary evaporator at 90° C. under a 10 mm Hg vacuum for 5 hours.The product is a light yellow, viscous liquid with the followingproperties: basicity, 1.682 meq/g; molecular weight by end grouptitration, 1716; Brookfield viscosity, 20,600 cps at 23° C. ¹³ C NMRshows the thiourea carbonyl carbon at 181.4 ppm and the amide carbonylcarbon at 172.3 ppm.

Example 17

Preparation of a Polymer Based on a 50:50 Weight Percent Blend ofJeffamine™ D-2000 and a Diamine Containing Four Urea Moieties perAverage Backbone Molecule

A small scale reaction injection molding (RIM) machine is used tofabricate parts suitable for physical property testing. The machineconsists of two chemical tanks (2-liter volume) and a pumping systemcapable of dispensing precise quantities of each component into amixhead where the components are rapidly mixed and sent through anaftermixer into a heated mold (4"×8"×0.125"). The following machineconditions are employed: component delivery pressure, 2000 psig (A and Bside); throughput, 35 lb/min; peanut aftermixter; mold temperature, 165°C.; demold time, 60 seconds; A side temperature, 35° C. to 38° C.; Bside temperature, 56° C. to 60° C.

A formulation is employed in which Isonate™ 143L (amethylene(diphenyldiisocyanate) which contains about 15 percent dimer; aproduct manufactured by The Dow Chemical Company) is used on the A sideand a blend of Jeffamine™ D-2000 (461.6 g), the product of Example1A(12) (461.6 g) and diethyltoluenediamine (576.8 g) are used on the BSide. An A:B weight ratio of 0.742 is used to produce a 60 volumepercent hard segment part at an index of 1.03. A series of well mixedparts are obtained having useful physical properties as shown in Example48. Properties are measured after the parts are allowed to age for 14days at ambient temperature or after the parts are post-cured for onehour at 175° C.

Example 18

Preparation of a Polymer Based on a Diamine Containing Four UreaMoieties per Average Backbone Molecule; Molecular Weight=1912.

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; peanutaftermixer; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 35° C. to 40° C.; B side temperature, 60° C. to 65° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand the product of Example 1A(12) (923.7 g) and diethyltoluenediamine(576.2 g) are used on the B side. An A:B weight ratio of 0.743 is usedto produce a 60 volume percent hard segment part at an index of 1.03. Aseries of well mixed parts are obtained having useful physicalproperties as shown in Example 48.

Example 19

Preparation of a Polymer Based on a Diamine Containing One Urea Moietyper Average Backbone Molecule; Molecular Weight=2562.

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side): throughput, 35 lb/min; peanutaftermixer; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 35° C. to 38° C.; B side temperature, 40° C. to 45° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand the product of Example 1B (915.4 g) and diethyltoluenediamine (584.6g) are used on the B side. An A:B weight ratio of 0.727 is used toproduce a 60 volume percent hard segment part at an index of 1.03. Aseries of well mixed parts are obtained having useful physicalproperties as shown in Example 48.

Example 20

Preparation of a Polymer Based on a Diamine Containing One Urea Moietyper Average Backbone Molecule; Molecular Weight=4120.

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side): throughput, 35 lb/min; peanutaftermixter; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 32° C. to 35° C.; B side temperature, 50° C. to 55° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand the product of Example 1C (906.8 g) and diethyltoluenediamine (593.2g) are used on the B side. An A:B weight ratio of 0.711 is used toproduce a 60 volume percent hard segment part at an index of 1.03. Aseries of well mixed parts are obtained having useful physicalproperties as shown in Example 48.

Example 21

Preparation of a Polymer Based on a Diamine Containing Four UreaMoieties per Average Backbone Molecule; Molecular Weight=9866.

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; peanutaftermixer; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 32° C. to 35° C.; B side temperature, 65° C. to 75° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand the product of Example 1A(1) (898.2 g) and diethyltoluenediamine(601.8 g) are used on the B side. An A:B weight ratio of 0.695 is usedto produce a 60 volume percent hard segment part at an index of 1.03. Aseries of well mixed parts are obtained having useful physicalproperties.

Example 22

Preparation of a Polymer Based on a 90:10 Weight Percent Blend ofJeffamine™ D-2000 and a Diamine Containing Four Biuret Moieties perAverage Backbone Molecule

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; peanutaftermixter; mold temperature, 165° C.; demold time, 60 seconds: A sidetemperature, 35° C. to 38° C.; B side temperature, 40° C. to 44° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand a blend of Jeffamine™ D-2000 (829.7 g), the product of Example 2A(92.2 g) and diethyltoluenediamine (578.1 g) are used on the B side. AnA:B weight ratio of 0.739 is used to produce a 60 volume percent hardsegment part at an index of 1.03. A series of well mixed parts areobtained having useful physical properties as shown in Example 48.

Example 23

Preparation of a Polymer Based on an 80:20 Weight Percent Blend ofJeffamine™ D-2000 and a Diamine Containing Four Biuret Moieties perAverage Backbone Molecule

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; peanutaftermixer; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 30° C. to 34° C.; B side temperature, 41° C. to 46° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand a blend of Jeffamine™ D-2000 (737.3 g), the product of Example 2A(184.3 g) and diethyltoluenediamine (578.3 g) is used on the B side. AnA:B weight ratio of 0.739 is used to produce a 60 volume percent hardsegment part at an index of 1.03. A series of well mixed parts areobtained having useful physical properties as shown in Example 48.

Example 24

Preparation of a Polymer Based on a 60:40 Weight Percent Blend ofJeffamine™ D-2000 and a Diamine Containing Four Biuret Moieties perAverage Backbone Molecule

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; peanutaftermixter; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 33° C. to 40° C.; B side temperature 42° C. to 53° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand a blend of Jeffamine™ D-2000 (552.7 g), the product of Example 2A(368.4 g) and diethyltoluenediamine (578.9 g) is used on the B side. AnA:B weight ratio of 0.738 is used to produce a 60 volume percent hardsegment part at an index of 1.03. A series of well mixed parts areobtained having useful physical properties as shown in Example 48.

Example 25

Preparation of a Polymer Based on a Diamine Containing Four BiuretMoieties per Average Backbone Molecule

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; peanutaftermixter; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 40° C. to 42° C.; B side temperature, 84° C. to 92° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand a blend of a diamine containing four biuret moieties per averagebackbone molecule (918.9 g, prepared by a procedure similar to that usedin Example 2A, molecular weight by end group titration is 2236) anddiethyltoluenediamine (581.1 g) are used on the B side. An A:B weightratio of 0.734 is used to produce a 60 volume percent hard segment partat an index of 1.03. A series of parts are obtained having usefulphysical properties as shown in Example 48.

Example 26

Preparation of a Polymer Based on a 50:50 Weight Percent Blend ofJeffamine™ D-2000 and a Diamine Containing Four Biuret Moieties perAverage Backbone Molecule and Having a Molecular Weight of 11,173

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixter; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 38° C. to 40° C.; B side temperature 75° C. to 85° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand a blend of Jeffamine™ D-2000 (455.4 g), the product of Example 6(455.4 g) and diethyltoluenediamine (589.3 g) are used on the B side. AnA:B weight ratio of 0.718 is used to produce a 60 volume percent hardsegment part at an index of 1.03. A series of well mixed parts areobtained having useful physical properties.

Example 27

Preparation of a Polymer Based on a Diamine Containing One Biuret Moietyper Average Backbone Molecule

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; peanutaftermixer mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 40° C. to 42° C.; B side temperature, 45° C. to 51° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand a blend of the diamine containing one biuret moiety per averagebackbone molecule prepared in Example 5 (913.7 g) anddiethyltoluenediamine (586.3 g) are used on the B side. An A:B weightratio of 0.724 is used to produce a 60 volume percent hard segment partat an index of 1.03. A series of well mixed parts are obtained havinguseful physical properties.

Example 28

Preparation of a Polymer Based on a Diamine Containing About ThreeThiourea Moieties per Average Backbone Molecule; Mold Temperature =120°C.

The same small scale reaction injection molding (RIM) machine is used tofabricate parts suitable for physical property testing that was used inExample 17. The following machine conditions are employed: componentdelivery pressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixer; mold temperature, 120° C.; demold time, 60 seconds; A sidetemperature, 33° C. to 36° C.; B side temperature, 73° C. to 78° C.

A formulation is employed in which Isonate™ 143L (amethylene(diphenyldiisocyanate) which contains about 155 dimer and asmall amount of highers; a product manufactured by The Dow ChemicalCompany) is used on the A side and a blend of the product of Example8(A) (918.8 g) and diethyltoluenediamine (581.2 g) are used on the Bside. An A:B weight ratio of 0.733 is used to produce 60 volume percenthard segment parts at an index of 1.03. The parts have very good greenstrength at demold. A series of well mixed parts are obtained havinguseful physical properties as shown hereinbelow.

Example 29

Preparation of a Polymer Based on 50/50 Weight Percent Blend ofJeffamine™ D-2000 and a Diamine Containing About Three Thiourea Moietiesper Average Backbone Molecule; Mold Temperature=120° C.

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixer; mold temperature, 120° C.; demold time, 60 seconds; A sidetemperature, 36° C. to 40° C.; B side temperature, 68° C. to 75° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand a blend of Jeffamine™ D-2000 (460.9 g; an aminated poly(propyleneglycol) of 1995 number average molecular weight, a product of Texaco),the product of Example 8(A) (460.9 g) and diethyltoluenediamine (578.3g) is used on the B side. An A:B weight ratio of 0.739 is used toproduce 60 volume percent hard segment parts at an index of 1.03. Theparts have good green strength at demold. A series of well mixed partsare obtained having useful physical properties as shown hereinbelow.Example 30

Preparation of a Polymer Based on a 50/50 Weight Percent Blend ofJeffamine™ D-2000 and a Diamine Containing About Three Thiourea Moietiesper Average Backbone Molecule; Mold Temperature=165° C.

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixer mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 36° C. to 40° C.; B side temperature, 68° C. to 75° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand a blend of Jeffamine™ D-2000 (460.9 g), the product of Example 8(A),and diethyltoluenediamine (578.3 g) is used on the B side. An A:B weightratio of 0.739 is used to produce 60 volume percent hard segment partsat an index of 1.03. The parts have excellent green strength at demold.A series of well mixed parts are obtained having useful physicalproperties as shown hereinbelow.

Example 31

Preparation of a Polymer Based on a Diamine Containing About FourThiourea Moieties per Average Backbone Molecule; Mold Temperature =165°C.

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixer; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 37° C. to 40° C.; B side temperature, 78° C. to 82° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand a blend of the product of Example 8(B) (895.9 g) anddiethyltoluenediamine (604.1 g) is used on the B side. An A:B weightratio of 0.690 is used to produce 60 volume percent hard segment partsat an index of 1.03. The parts have relatively poor green strength atdemold; some cracking occurs in the mold. A series of well mixed partsare obtained.

Comparative Example 1

Preparation of a Polymer Based on Jeffamine™ D-2000; MoldTemperature=120° C.

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixter; mold temperature, 120° C.; demold time, 60 seconds; A sidetemperature, 29° C. to 32° C.; B side temperature, 67° C. to 75° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand a blend of Jeffamine™ D-2000 (921.6 g) and diethyltoluenediamine(578.4 g) is used on the B side. An A:B weight ratio of 0.739 is used toproduce 60 volume percent hard segment parts at an index of 1.03. Theparts have extremely poor green strength at demold; multiple crackingoccurs in the mold making property testing impossible.

Comparative Example 2

Preparation of a Polymer Based on Jeffamine™ D-2000; MoldTemperature=165° C.

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixter; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 29° C. to 32° C.; B side temperature, 7° C. to 75° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand a blend of Jeffamine™ D-2000 (921.6 g) and diethyltoluenediamine(578.4 g) is used on the B side. An A:B weight ratio of 0.739 is used toproduce 60 volume percent hard segment parts at an index of 1.03. Theparts have marginal poor green strength at demold and must be handledvery carefully to prevent cracking.

Example 32

Preparation of a Polymer Based on a 50:50 Weight Percent Blend ofJeffamine™ D-2000 and a Diamine Containing Six Amide Moieties perAverage Backbone Molecule

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixter; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 30° C. to 39° C.; B side temperature, 80° C. to 85° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand a mixture of Jeffamine™ D-2000 (461.8 g), the polyamide diamine ofExample 1E (461.8 g) and diethyltoluenediamine (575.4 g) are used on theB side. An A:B weight ratio of 0.742 is used to produce a 60 volumepercent hard segment part at an index of 1.03. A series of well mixedparts are obtained having useful physical properties as shown in Example48.

Example 33

Preparation of a Polymer Based on a 75:25 Weight Percent Blend ofJeffamine™ D-2000 and a Diamine Containing Six Amide Moieties perAverage Backbone Molecule

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixter; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 36° C. to 38° C.; B side temperature, 80 ° C. to 88° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand a blend of Jeffamine™ D-2000 (692.5 g), the product of Example 1E(230.8 g) and diethyltoluenediamine (576.6 g) is used on the B side. AnA:B weight ratio of 0.742 is used to produce a 60 volume percent hardsegment part at an index of 1.03. A series of well mixed parts areobtained having useful physical properties as shown in Example 48.

Example 34

Preparation of a Polymer Based on a 90:10 Weight Percent Blend ofJeffamine™ D-2000 and a Diamine Containing Six Amide Moieties perAverage Backbone Molecule

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixer; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 35° C. to 38° C.; B side temperature, 62° C. to 69° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand a blend of Jeffamine™ D-2000 (831.0 g), the product of Example 1E(92.3 g) and diethyltoluenediamine (576.7 g) are used on the B side. AnA:B weight ratio of 0.742 is used to produce a 60 volume percent hardsegment part at an index of 1.03. A series of well mixed parts areobtained having useful physical properties as shown in Example 48.

Example 35

Preparation of a Polymer Based on a Diamine Containing Two BiuretMoieties and One Urea Moiety per Average Backbone Molecule

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; peanutaftermixer; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 30° C. to 35° C.; B side temperature, 95° C. to 105° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand a mixture of the product of Example 10 (924.6 g) anddiethyltoluenediamine (575.4 g) are used on the B side. An A:B weightratio of 0.744 is used to produce a 60 volume percent hard segment partat an index of 1.03. A series of well mixed parts are obtained havinguseful physical properties as shown in Example 48.

Example 36

Preparation of a Polymer Based on a 50:50 Weight Percent Mixture ofJeffamine™ D-2000 and a Diamine Containing Two Biuret Moieties and OneUrea Moiety per Average Backbone Molecule

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; peanutaftermixer; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 30° C. to 35° C.; B side temperature, 70° C. to 80° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand a mixture of the product of Example 10 (461.7 g), Jeffamine™ D-2000(461.7 g) and diethyltoluenediamine (575.4 g) are used on the B side. AnA:B weight ratio of 0.742 is used to produce a 60 volume percent hardsegment part at an index of 1.03. A series of well mixed parts areobtained having useful physical properties as shown in Example 48.

Example 37

Preparation of Polymers Based on a Diamine Containing Eight AmideMoieties per Average Backbone Molecule

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixter; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 30° C. to 35° C.; B side temperature, 76° C. to 81° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand the product of Example 1E (914.5 g) and diethyltoluenediamine (585.5g) are used on the B side. An A:B weight ratio of 0.725 is used toproduce a 60 volume percent hard segment part at an index of 1.03. Theparts are very tough at demold and have excellent green strength. Aseries of well mixed parts are obtained having useful physicalproperties as shown in Example 48.

The above experiment is repeated using a mold temperature of 120° C.Parts are produced having good green strength at demold. The aboveexperiment is repeated using a mold temperature of 100° C. Greenstrength is still sufficient to produce good parts without cracking.This experiment demonstrates that the mold temperature can be loweredconsiderably by using some of the compositions of this invention.

Example 38

Preparation of Polymers Based on a Diamine Containing Eight AmideMoieties per Average Backbone Molecule; Molecular Weight=4828.

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixter; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 38° C. to 42° C.; B side temperature, 75° C. to 82° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand the product of Example 1K (903.5 g) and diethyltoluenediamine (596.5g) are used on the B side. An A:B weight ratio of 0.705 is used toproduce a 60 volume percent hard segment part at an index of 1.03. Theparts are very tough at demold and have excellent green strength. Aseries of well mixed parts are obtained having useful physicalproperties as shown in Example 48.

Example 39

Preparation of Polymers Based on a Diamine Containing Eight AmideMoieties per Average Backbone Molecule; Molecular Weight=5565.

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixer; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 35° C. to 40° C.; B side temperature, 78° C. to 85° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand the product of Example 1L (901.8 g) and diethyltoluenediamine (598.2g) are used on the B side. An A:B weight ratio of 0.701 is used toproduce a 60 volume percent hard segment part at an index of 1.03. Theparts are very tough at demold and have excellent green strength. Aseries of well mixed parts are obtained having useful physicalproperties as shown in Example 48.

Example 40

Preparation of Polymers Based on a Diamine Containing Eight AmideMoieties per Average Backbone Molecule Molecular Weight=7282.

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixter; mold temperature, 165° C.; demold time, 60 seconds; A sidetemperature, 37° C. to 41° C.; B side temperature, 75° C. to 81° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand the product of Example 1M (899.3 g) and diethyltoluenediamine (600.7g) are used on the B side. An A:B weight ratio of 0.697 is used toproduce a 60 volume percent hard segment part at an index of 1.03. Theparts are very tough at demold and have excellent green strength. Aseries of well mixed parts are obtained having useful physicalproperties as shown in Example 48.

Example 41

Preparation of Polymers Based on a Diamine Containing Eight AmideMoieties per Average Backbone Molecule; Molecular Weight=9289.

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixter; mold temperature, 165° C.; demold time, 8 seconds; A sidetemperature, 42° C. to 46° C.; B side temperature, 73° C. to 78° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand the product of Example 1P (897.6 g) and diethyltoluenediamine (602.4g) are used on the B side. An A:B weight ratio of 0.697 is used toproduce a 60 volume percent hard segment part at an index of 1.03. Aseries of well mixed parts are obtained having useful physicalproperties as shown in Example 48.

Example 42

Preparation of Polymers Based on a Diamine Containing Five AmideMoieties per Average Backbone Molecule; Molecular Weight=7909.

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixer; mold temperature, 165° C.; demold time, 8 seconds; A sidetemperature, 36° C. to 40° C.; B side temperature, 68° C. to 74° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand the product of Example 1N (898.7 g) and diethyltoluenediamine (601.3g) are used on the B side. An A:B weight ratio of 0.696 is used toproduce a 60 volume percent hard segment part at an index of 1.03. Aseries of well mixed parts are obtained having useful physicalproperties as shown in Example 48.

Example 43

Preparation of Polymers Based on a Diamine Containing Four Urea Moietiesper Average Backbone Molecule; Molecular Weight=3367.

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixer; mold temperature, 165° C.; demold time, 8 seconds; A sidetemperature, 38° C. to 40° C.; B side temperature, 75° C. to 80° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand the product of Example 1A(6) (908.9 g) and diethyltoluenediamine(591.1 g) are used on the B side. An A:B weight ratio of 0.715 is usedto produce a 60 volume percent hard segment part at an index of 1.03. Aseries of well mixed parts are obtained having useful physicalproperties as shown in Example 48.

Example 44

Preparation of Polymers Based on a Diamine Containing Four Urea Moietiesper Average Backbone Molecule; Molecular Weight=4710.

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixer; mold temperature, 165° C.; demold time, 8 seconds; A sidetemperature, 40° C. to 42° C.; B side temperature, 76° C. to 82° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand the product of Example 1A(7) (903.8 g) and diethyltoluenediamine(596.2 g) are used on the B side. An A:B weight ratio of 0.705 is usedto produce a 60 volume percent hard segment part at an index of 1.03. Aseries of well mixed parts are obtained having useful physicalproperties as shown in Example 48.

Example 45

Preparation of Polymers Based on a Diamine Containing Four Urea Moietiesper Average Backbone Molecule; Molecular Weight=6326.

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixter; mold temperature, 165° C.; demold time, 8 seconds; A sidetemperature, 35° C. to 42° C.; B side temperature, 82° C. to 88° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand the product of Example 1A(8) (900.5 g) and diethyltoluenediamine(599.5 g) are used on the B side. An A:B weight ratio of 0.699 is usedto produce a 60 volume percent hard segment part at an index of 1.03. Aseries of well mixed parts are obtained having useful physicalproperties as shown in Example 48.

Example 46

Preparation of Polymers Based on a Diamine Containing Four Urea Moietiesper Average Backbone Molecule; Molecular Weight=11,119.

The same small scale RIM equipment is used that was used in Example 17.The following machine conditions are employed: component deliverypressure, 2000 psig (A and B side); throughput, 35 lb/min; harpaftermixer; mold temperature, 165° C.; demold time, 8 seconds; A sidetemperature, 44° C. to 47° C.; B side temperature, 62° C. to 68° C.

A formulation is employed in which Isonate™ 143L is used on the A sideand the product of Example 1A(9) (896.5 g) and diethyltoluenediamine(603.5 g) are used on the B side. An A:B weight ratio of 0.691 is usedto produce a 60 volume percent hard segment part at an index of 1.03. Aseries of well mixed parts are obtained having useful physicalproperties as shown in Example 48.

Example 47

Preparation of a Polymer Based on a Diamine Containing About Three UreaMoieties per Average Backbone Molecule

The same small scale reaction injection molding (RIM) machine is used tofabricate parts that was used in Example 17. The following machineconditions are employed component delivery pressures, 2000 psig (A and Bside); throughput, 35 lb/min; harp aftermixer; mold temperature, 165°C.; demold time, 60 seconds; A side temperature, 38° C. to 40° C.; Bside temperature, 75° C. to 80° C.

A formulation is employed in which Isonate™ 143L (1072.5 g) is used onthe A side and a blend of the product of Example 1A(6) (908.9 g) anddiethyltoluenediamine (591.1 g) are used on the B-side. An A:B weightratio of 0.715 is used to produce a 60 volume percent hard segment partat an index of 1.03. A series of well mixed parts are obtained havinguseful physical properties.

Example 48

Measurement of Physical Properties

Plaques are cured for two weeks at ambient temperature or post-cured forone hour at 175° C. prior to physical testing. Properties are comparedrelative to Jeffamine™ D-2000, since D-2000 has the samepolypropyleneoxy backbone, the same primary amino end groups andapproximately the same molecular weight as many of the novelcompositions of this invention. Results are given in Tables I, II, andIII.

Example 49

Preparation of a Diamine Containing About Seven Urea Moieties in itsBackbone Based on Jeffamine™ D-400 and 2-Methyl-1,5-pentanediamine; 5:1Molar Ratio

Jeffamine™ D-400 (690.0 g, 1.500 moles, MW=460, an aminatedpoly(propylene glycol) manufactured by Texaco),2-methyl-1,5-pentanediamine (34.87 g, 0.300 mole) and urea (99.12 g,1.650 moles) are combined in a 1000-ml reactor equipped with an overheadstirrer, thermometer, condenser, and temperature controller andmaintained under a nitrogen atmosphere. The reactor is heated at 150° C.for 28 hours. The product is obtained as a viscous liquid: Brookfieldviscosity=436,000 cps at 22° C.; 0.6223 meq amine/g and 6.9 ureamoieties/molecule by titration with 0.1 N HClO₄ ; calculated averagemolecular weight is 3214 by end group titration. Carbon-13 NMR (DMSO-d₆)shows urea carbonyls (157.4 ppm, D-400/D-400 urea; 158.0/158.1 ppm,D-400/2-Me-PDA urea; and 158.6 ppm, 2-Me-PDA/2-Me-PDA urea).

This example shows the preparation of a diamine product which containsthree different kinds of urea moieties in its backbone. The differenturea moieties result from the two different diamines used in itspreparation.

Example 50

Preparation of a Diamine Containing About Three Urea Moieties in itsBackbone Based on Jeffamine™ D-400 and 2-Methyl-1,5-pentanediamine; 5:1Molar Ratio

Jeffamine™ D-400 (230.0 g, 0.500 mole), 2-methyl-1,5-pentanediamine(11.67 g, 0.100 mole) and urea (30.03 g, 0.500 mole) are combined in thesame reaction setup used in Example 49, except a 500-ml reactor is used.The reactor is heated at 150° C. for 23 hours. The product is obtainedas a viscous liquid: Brookfield viscosity=47,250 cps at 22° C.; 1.2009meq amine/g and 3.2 urea moieties/molecule by titration with 0.1 N HClO₄; calculated average molecular weight is 1666 by end group titration.Carbon-13 NMR (DMSO-d₆) shows urea carbonyls (157.4 ppm, D-400/D-400urea; 158.0/158.1 ppm, D-400/2-Me-PDA urea; and 158.6 ppm,2-Me-PDA/2-Me-PDA urea).

This example shows the preparation of a diamine product which containsthree different kinds of urea moieties in its backbone. The differenturea moieties result from the two different diamines used in itspreparation.

Example 51

Preparation of a Diamine Containing About Four Urea Moieties in itsBackbone Based on Jeffamine™ D-400 and 2-Methyl-1,5-pentanediamine; 11:1Molar Ratio

Jeffamine™ D-400 (253.05 g, 0.550 mole), 2-methyl-1,5-pentanediamine(5.84 g, 0.050 mole) and urea (30.04 g, 0.500 mole) are combined in thesame reaction setup used in Example 50. The reactor is heated at 150° C.for 24 hours. The product is obtained as a viscous liquid: Brookfieldviscosity=130,400 cps at 22° C.; 0.8604 meq amine/g and 4.2 ureamoieties/molecule by titration with 0.1 N HClO₄ ; calculated averagemolecular weight is 2325 by end group titration. Carbon-13 NMR (DMSO-d₆)shows urea carbonyls (157.4 ppm, D-400/D-400 urea; 158.0/158.1 ppm,D-400/2-Me-PDA urea; and 158.6 ppm, 2-Me-PDA/2-Me-PDA urea).

This example shows the preparation of a diamine product which containsthree different kinds of urea moieties in its backbone. The differenturea moieties result from the two different diamines used in itspreparation.

Example 52

Preparation of a Diamine Containing About Six Urea Moieties in itsBackbone Based on Jeffamine™ D-400 and 2-Methyl-1,5-pentanediamine;0.83:1 Molar Ratio

Jeffamine™ D-400 (115.05 g, 0.250 mole), 2-methyl-1,5-pentanediamine(34.87 g, 0.300 mole) and urea (30.07 g, 0.500 mole) are combined in thesame reaction setup used in Example 50. The reactor is heated at 150° C.for 22 hours. The product is obtained as a viscous liquid: Brookfieldviscosity=>2,000,000 cps at 22° C.; 0.9042 meq amine/g by titration with0.1 N HClO₄ ; calculated average molecular weight is 2212 by end grouptitration. Carbon-13 NMR (DMSO-d₆) shows urea carbonyls (157.5 ppm,D-400/D-400 urea; 158.1/158.2 ppm, D-400/2-Me-PDA urea; and 158.8 ppm,2-Me-PDA/2-Me-PDA urea).

This example shows the preparation of a diamine product which containsthree different kinds of urea moieties in its backbone. The differenturea moieties result from the two different diamines used in itspreparation.

Example 53

Preparation of a Diamine Containing About Twenty Urea Moieties in itsBackbone Based on Jeffamine™ D-400 and 2-Methyl-1,5-pentanediamine;0.20:1 Molar Ratio

Jeffamine™ D-400 (92.12 g, 0.200 mole), 2-methyl-1,5-pentanediamine(116.21 g, 1.000 mole) and urea (68.67 g, 1.143 moles) are combined inthe same reaction setup used in Example 50. The reactor is heated at150° C. for 24 hours. The product is obtained as a viscous liquid:Brookfield viscosity=>2,000,000 cps at 22° C.; 0.6045 meq amine/g bytitration with 0.1 N HClO₄ ; calculated average molecular weight is 3309by end group titration. Carbon-13 NMR (DMSO-d₆) shows urea carbonyls(157.4 ppm, D-400/D-400 urea; 158.0/158.1 ppm, D-400/2-Me-PDA urea; and158.6 ppm, 2-Me-PDA/2-Me-PDA urea).

This example shows the preparation of a diamine product which containsthree different kinds of urea moieties in its backbone. The differenturea moieties result from the two different diamines used in itspreparation.

Example 54

Preparation of a Diamine Containing About Four Urea Moieties in itsBackbone Based on Jeffamine™ D-400 and 1,6-Hexanediamine; 11:1 MolarRatio

Jeffamine™ D-400 (253.09 g, 0.550 mole), 1,6-hexanediamine (5.87 g,0.050 mole) and urea (30.05 g 0.500 mole) are combined in the samereaction setup used in Example 50. The reactor is heated at 150° C. for24 hours. The product is obtained as a viscous liquid: Brookfieldviscosity=>2,000,000 cps at 22° C.; 0.9075 meq amine/g and 4.0 ureamoieties/molecule by titration with 0.1 N HClO₄ ; calculated averagemolecular weight is 2204 by end group titration. Carbon-13 NMR (DMSO-d₆)shows urea carbonyls (157.4 ppm, D-400/D-400 urea; 157.9 ppm, D-400/HDAurea; and 158.6 ppm, HDA/HDA urea).

This example shows the preparation of a diamine product which containsthree different kinds of urea moieties in its backbone. The differenturea moieties result from the two different diamines used in itspreparation.

Example 55

Preparation of a Diamine Containing About Five Urea Moieties in itsBackbone Based on Jeffamine™ D-400 and 1,6-Hexanediamine; 5:1 MolarRatio

Jeffamine™ D-400 (230.01 g, 0.500 mole), 1,6-hexanediamine (11.67 g,0.100 mole) and urea (30.03 g, 0.500 mole) are combined in the samereaction setup used in Example 50. The reactor is heated at 150° C. for24 hours. The product is obtained as a viscous liquid: Brookfieldviscosity=>2,000,000 cps at 22° C.; 1.1189 meq amine/g by titration with0.1 N HClO₄ ; calculated average molecular weight is 1787 by end grouptitration. Carbon-13 NMR (DMSO-d₆) shows urea carbonyls (157.4 ppm,D-400/D-400 urea; 158.0 ppm, D-400/HDA urea; and 158.7 ppm, HDA/HDAurea).

This example shows the preparation of a diamine product which containsthree different kinds of urea moieties in its backbone. The differenturea moieties result from the two different diamines used in itspreparation.

Example 56

Preparation of a Diamine Containing About Four Urea Moieties in itsBackbone Based on Jeffamine™ D-400 and 2,4-Diaminotoluene; 11:1 MolarRatio

Jeffamine™ D-400 (253.02 g, 0.550 mole), 2,4toluenediamine (6.11 g,0.050 mole) and urea (30.04 g, 0.500 mole) are combined in the samereaction setup used in Example 50. The reactor is heated at 150° C. for25 hours. The product is obtained as a viscous liquid: Brookfieldviscosity=153,600 cps at 22° C.; 0.9073 meq amine/g by titration with0.1 N HClO₄ ; calculated average molecular weight is 2204 by end grouptitration. Carbon-13 NMR (DMSO-d₆) shows urea carbonyls (157.4 ppm and158.6 ppm). This example shows the preparation of a diamine productwhich contains aromatic urea moieties in its backbone.

Example 57

Preparation of a Diamine Containing About Six Urea Moieties in itsBackbone Based on Jeffamine™ D-400 and 2,4-Diaminotoluene; 5:1 MolarRatio

Jeffamine™ D-400 (230.02 g, 0.500 mole), 2,4toluenediamine (12.23 g,0.100 mole) and urea (32.21 g, 0.536 mole) are combined in the samereaction setup used in Example 50. The reactor is heated at 150° C. for24 hours. The product is obtained as a viscous liquid: Brookfieldviscosity=715,600 cps at 22° C.; 0.7809 meq amine/g by titration with0.1 N HClO₄ ; calculated average molecular weight is 2561 by end grouptitration. Carbon-13 NMR (DMSO-d₆) shows urea carbonyls (157.4 ppm and158.6 ppm). This example shows the preparation of a diamine productwhich contains aromatic urea moieties in its backbone.

Example 58

Preparation of a Diamine Containing About Four Urea and Four BiuretMoieties in its Backbone Based on Jeffamine™ D-400 and2-Methyl-1,5-pentanediamine; 0.83:1 Molar Ratio

Jeffamine™ D-400 (115.05 g, 0.250 mole), 2-methyl-1,5-pentanediamine(34.87 g, 0.300 mole), biuret (25.77 g, 0.250 mole) and urea (15.02 g,0.250 mole) are combined in the same reaction setup used in Example 50.The reactor is heated at 150° C. for 24 hours. The product is obtainedas a viscous liquid: Brookfield viscosity=>2,000,000 cps at 22° C.;0.5751 meq amine/g by titration with 0.1 N HClO₄ ; calculated averagemolecular weight is 3478 by end group titration. Carbon-13 NMR (DMSO-d₆)shows urea carbonyls (157.6 ppm, D-400/D-400 urea; 158.3/158.4 ppm,D-400/2-Me-PDA urea; and 158.9 ppm, 2-Me-PDA/2-Me-PDA urea) and biuretcarbonyls (154.5 ppm, D-400/D-400 biuret; and 155.0-155.5 ppm,D-400/2-Me-PDA biuret and 2-Me-PDA/2-Me-PDA biuret).

This example shows the preparation of a diamine product which containsthree different kinds of biuret moieties in its backbone. These moietiesresult from the two different diamines and two differentcarbonyl-containing materials used in its preparation.

Example 59

Preparation of a Diamine Containing About Eight Biuret Moieties in itsBackbone Based on Jeffamine™ D-400 and 2-Methyl-1,5-pentanediamine;0.83:1 Molar Ratio

Jeffamine™ D-400 (115.09 g, 0.250 mole), 2-methyl-1,5-pentanediamine(34.89 g, 0.300 mole) and biuret (51.55 g, 0.500 mole) are combined inthe same reaction setup used in Example 50. The reactor is heated at150° C. for 24 hours. The product is obtained as a viscous liquid:Brookfield viscosity=>2,000,000 ps at 22° C.; 0.5573 meq amine/g bytitration with 0.1 N HClO₄ ; calculated average molecular weight is 3589by end group titration. Carbon-13 NMR (DMSO-d₆) shows biuret carbonyls(154.5 ppm, D-400/D-400 biuret; and 154.9-155.4 ppm, D-400/2-Me-PDAbiuret and 2-Me-PDA/-2-Me-PDA biuret).

This example shows the preparation of a diamine product which containsthree different kinds of biuret moieties in its backbone. The differentbiuret moieties result from the two different diamines used in itspreparation.

Example 60

Preparation of a Diamine Containing About Ten Amide Moieties in itsBackbone Based on Jeffamine™ D-400 and 2-Methyl-1,5-pentanediamine; 5:1Molar Ratio

Jeffamine™ D-400 (230.00 g, 0.500 mole), 2-methyl-1,5-pentanediamine(11.69 g, 0.100 mole) and adipic acid (73.09 g, 0.500 mole) are combinedin the same reaction setup used in Example 50, except that a Dean Starkwater trap is added between the reactor and condenser. The reactor isheated at 120° C. for 1 hour to form the corresponding salt. Toluene (50ml) is added and the system is heated at reflux (175° C) for 24 hours.Toluene is removed at reduced pressure (2 hr/150° C./1 mm Hg). Theproduct is obtained as a viscous liquid: Brookfield viscosity=>2,000,000cps at 22° C.; 0.7046 meq amine/g by titration with 0.1 N HClO₄ ;calculated average molecular weight is 2838 by end group titration.Carbon-13 NMR (DMSO-d₆) shows amide carbonyls (171.8 ppm, D-400 amide;and 172.2/172.4 ppm, 2-Me-PDA amide).

This example shows the preparation of a diamine product which containstwo different kinds of amide moieties in its backbone. The differentamide moieties result from the two different diamines used in itspreparation.

Example 61

Preparation of a Diamine Containing About Twelve Amide Moieties in itsBackbone Based on Jeffamine™ D-400 and 2-Methyl-1,5-pentanediamine; 5:1Molar Ratio

Jeffamine™ D-400 (460.00 g, 1.000 mole), 2-methyl-1,5-pentanediamine(23.26 g, 0.200 mole) and adipic acid (140.31 g, 0.960 mole) arecombined in the same reaction setup used in Example 60, except that aone-liter reactor is used. The reactor is heated at 120° C. for 1 hourto form the corresponding salt. Toluene (75 ml) is added and the systemis heated at reflux (165° C.) for 24 hours. Toluene is removed atreduced pressure (2 hr/150° C./1 mm Hg). The product is obtained as aviscous liquid: Brookfield viscosity=>2,000,000 cps at 22° C.; 0.8330meq amine/g by titration with 0.1 N HClO₄ ; calculated average molecularweight is 2401 by end group titration. Carbon-13 NMR (DMSO-d6) showsamide carbonyls (171.8 ppm, D-400 amide; and 172.2/172.4 ppm, 2-Me-PDAamide).

This example shows the preparation of a diamine product which containstwo different kinds of amide moieties in its backbone. The differentamide moieties result from the two different diamines used in itspreparation.

Example 62

Preparation of a Diamine Containing About Twenty-Four Amide Moieties inits Backbone Based on Jeffamine™ D-400 and 2-Methyl-1,5-pentanediamine;0.83:1 Molar Ratio

Jeffamine™ D-400 (115.09 g, 0.250 mole), 2-methyl-1,5-pentanediamine(34.90 g, 0.300 mole) and adipic acid (73.09 g, 0.500 mole) are combinedin the same reaction setup used in Example 60. The reactor is heated at120° C. for 1 hour to form the corresponding salt. Toluene (50 ml) isadded and the system is heated at reflux (175° C.) for 24 hours. Tolueneis removed at reduced pressure (2 hr/150° C./1 mm Hg). The product isobtained as a viscous liquid: Brookfield viscosity=>2,000,000 cps at 22°C.; 0.4684 meq amine/g by titration with 0 1 N HClO₄ ; calculatedaverage molecular weight is 4270 by end group titration. Carbon-13 NMR(DMSO-d6) shows amide carbonyls (171.9 ppm, D-400 amide; and 172.3/172.5ppm, 2-Me-PDA amide).

This example shows the preparation of a diamine product which containstwo different kinds of amide moieties in its backbone. The differentamide moieties result from the two different diamines used in itspreparation.

Example 63

Preparation of a Diamine Containing About Two Thiourea Moieties in itsBackbone Based on Jeffamine™ D-400 and 2-Methyl-1,5-pentanediamine; 5:1Molar Ratio

Jeffamine™ D-400 (230.04 g, 0.500 mole), 2-methyl-1,5-pentanediamine(11.62 g, 0.100 mole) and thiourea (38.07 g, 0.500 mole) are combined inthe same reaction setup used in Example 50. The reactor is heated at150° C. for 23 hours. The product is obtained as a viscous liquid:Brookfield viscosity=76,100 cps at 22° C.; 1.414 meq amine/g and 2.3thiourea moieties/-molecule by titration with 0.1 N HClO₄ ; calculatedaverage molecular weight is 1414 by end group titration. Carbon-13 NMR(DMSO-d₆) shows thiourea carbonyls (181.7 ppm, D-400/D-400 thiourea; anda broad band from 182.0-183.0 ppm, D-400/2-Me-PDA thiourea and2-Me-PDA/2-Me-PDA thiourea).

This example shows the preparation of a diamine product which containsthree different kinds of thiourea moieties in its backbone. Thedifferent thiourea moieties result from the two different diamines usedin its preparation.

The addition of urea, thiourea, biuret and/or amide moieties into thediamine backbone produces polymers which have superior green strength atdemold (much less brittle than plaques without these moieties). Theyalso have greatly increased modulus, toughness and strength properties(see Table I) in many cases. Solvent resistance and hardness are alsogreatly increased (see Table II). Impact properties are reduced in somecases, but post-curing restores many of these properties in Dynatupmeasurements (see Table III).

It is understood that various other modifications will be apparent alsoand can readily be made by those skilled in the art without departingfrom the scope of the invention. Accordingly, it is not intended thatthe scope of the claims appended hereto be limited to the description asset forth herein, but rather that the claims be construed asencompassing all the features of patentable novelty which reside in thepresent invention, including all the features which would be consideredas equivalents thereof by those skilled in the art to which thisinvention pertains.

                                      TABLE I                                     __________________________________________________________________________    Tensile and Modulus Properties of Polymers Based on Backbone                  Modified Diamines and Blends with D-2000                                      Plaque                                                                        from Post-                                                                              Flexural                                                                            Youngs                                                                              Yield                                                                              Yield                                                                              Ultimate                                                                           Ultimate                                 Example                                                                            Cured.sup. 1                                                                       Modulus.sup. 2                                                                      Modulus.sup. 3                                                                      Stress.sup. 3                                                                      Strain.sup. 3                                                                      Stress.sup. 3                                                                      Strain.sup. 3                            __________________________________________________________________________    C*   no   142,800                                                                             160,000                                                                             6240 11.1 6020 18.2                                          yes  153,750                                                                             170,000                                                                             6680 11.3 6510 16.8                                     17   no   214,750                                                                             280,000                                                                             8540 10.2 8280 8.3                                           yes  227,000                                                                             285,000                                                                             8540 10.5 8400 10.8                                     18   no   284,000                                                                             320,000                                                                             --   --   6350 2.4                                           yes  290,750                                                                             322,000                                                                             6750  2.8 10400                                                                              9.9                                      19   no   131,300                                                                             175,000                                                                             5970 12.6 5790 13.0                                          yes  140,800                                                                             185,000                                                                             6520 13.5 6500 13.8                                     20   no   120,000                                                                             125,000                                                                             NO   NO   4320 7.2                                           yes  126,000                                                                             130,000                                                                             5030 14.4 4980 13.1                                     22   no   160,750                                                                             175,000                                                                             6320 11.0 6110 13.8                                          yes  179,750                                                                             177,500                                                                             6730 10.7 6575 13.7                                     23   no   178,500                                                                             190,000                                                                             6820 10.9 6580 12.9                                          yes  180,700                                                                             195,000                                                                             6840 10.3 6630 13.6                                     24   no   198,250                                                                             220,000                                                                             7700 10.5 7300 14.5                                          yes  210,300                                                                             225,000                                                                             7780 10.0 7510 16.3                                     25   no   361,500                                                                             ND    ND   ND   ND   ND                                            yes  400,000                                                                             ND    ND   ND   ND   ND                                       28   no   285,000                                                                             TB    TB   TB   TB   TB                                            yes  286,000                                                                             280,000                                                                             NO   NO   2280 0.6                                      29   no   220,000                                                                             ND    ND   ND   ND   ND                                       30   no   230,000                                                                             230,000                                                                             NO   NO   3490 1.6                                           yes  240,000                                                                             242,000                                                                             2560  1.7 5870 15.5                                     32   no   245,750                                                                             270,000                                                                             7935 10.7 7780 13.3                                          yes  255,500                                                                             290,000                                                                             9430  9.9 9270 15.1                                     33   no   199,250                                                                             220,000                                                                             6680 10.5 6570 12.7                                          yes  259,000                                                                             250,000                                                                             8150 10.2 7910 12.9                                     34   no   179,000                                                                             195,000                                                                             6240 11.0 5890 12.6                                          yes  185,750                                                                             228,000                                                                             7690 10.7 7420 11.9                                     35   no   318,500                                                                             335,000                                                                             9310  9.4 8550 9.8                                           yes  334,250                                                                             380,000                                                                             9900  5.1 9680 7.3                                      36   no   211,300                                                                             260,000                                                                             8230 10.3 8070 13.1                                          yes  235,300                                                                             270,000                                                                             8640 10.5 8480 13.0                                     CE 1**                                                                             no   167,000                                                                             200,000                                                                             6940 10.7 6770 14.6                                          yes  199,000                                                                             220,000                                                                             7475 10.6 7210 16.6                                     37   no   300,000                                                                             300,000                                                                             NO   NO   6230 2.4                                           yes  350,000                                                                             355,000                                                                             NO   NO   10,800                                                                             8.0                                      38   no   220,000                                                                             200,000                                                                             NO   NO   6450 5.8                                           yes  220,000                                                                             240,000                                                                             7950  9.0 7740 9.3                                      39   no   172,000                                                                             170,000                                                                             NO   NO   5195 4.8                                           yes  185,000                                                                             190,000                                                                             3580  0.5 6315 6.5                                      40   no   136,000                                                                             150,000                                                                             NO   NO   4120 5.8                                           yes  148,000                                                                             160,000                                                                             NO   NO   4680 6.6                                      41   no    88,000                                                                              95,000                                                                             NO   NO   5620 6.0                                           yes   98,000                                                                             120,000                                                                             NO   NO   2500 3.6                                      42   no    87,000                                                                             100,000                                                                             NO   NO   7250 6.7                                           yes   94,000                                                                             120,000                                                                             NO   NO   3200 4.7                                      43   no   210,000                                                                             227,000                                                                             NO   NO   6440 3.9                                           yes  220,000                                                                             240,000                                                                             7440  8.4 7620 10.9                                     44   no   172,000                                                                             180,000                                                                             NO   NO   3440 2.0                                           yes  185,000                                                                             185,000                                                                             NO   NO   5860 5.5                                      45   no   136,000                                                                             150,000                                                                             NO   NO   3400 3.0                                           yes  148,000                                                                             160,000                                                                             NO   NO   4150 6.0                                      46   no    80,000                                                                              95,000                                                                             NO   NO   2950 7.8                                           yes   90,000                                                                             100,000                                                                             NO   NO   1566 5.3                                      __________________________________________________________________________     .sup. 1 Postcured at 175° C. for one hour                              .sup. 2 ASTM D790                                                             .sup.  3 ASTM D638                                                            *Sample is not an example of the invention. Jeffamine D2000 is substitute     for the polyamine component in the formulation of Example 11                  NO = not observed                                                             ND = not determined                                                           TB = too brittle                                                              **Comparative Example 1  not an example of this invention                

                  TABLE II                                                        ______________________________________                                        Hardness and Solvent Resistance Properties of Polymers Based                  on Backbone-Modified Diamines and Blends with D-2000                                                Solvent Resistance                                      Plaque                (% weight gain after 6 days).sup.3                      from   Post-    Hardness.sup. 2                                                                         Wa-  Meth- Tolu-                                    Example                                                                              Cured.sup. 1                                                                           (Shore D) ter  anol  ene   MEK                                ______________________________________                                        C*     no       75        1.4  22.8  10.2  24.2                                      yes      76        1.2  21.2  11.9  31.4                               17     no       76        1.2  16.2   2.9  11.1                                      yes      77        1.2  13.5   1.8   8.3                               18     no       85        0.3  12.2   0.3   2.3                                      yes      85        0.3  11.4   0.3   1.9                               19     no       73        1.5  26.2  11.7  41.0                                      yes      75        1.6  25.6   9.6  33.7                               20     no       58        2.1  32.5  30.7  45.6                                      yes      58        2.2  30.8  28.6  42.3                               22     no       75        1.6  22.6  11.3  23.5                                      yes      79        ND   ND    ND    ND                                 23     no       77        1.4  22.1   7.7  19.6                                      yes      78        ND   ND    ND    ND                                 24     no       77        1.2  20.2   4.1  18.3                                      yes      78        ND   ND    ND    ND                                 25     no       82        0.8  13.0   0.4   6.0                                      yes      84        0.8  11.4   0.2   2.5                               28     no       63        1.0  17.1   0.4  14.3                                      yes      67        0.9  11.8   0.3   5.0                               29     no       62        ND   ND    ND    ND                                 30     no       64        1.4  18.5   3.4  16.9                                      yes      60        1.3  15.4   1.7  10.6                               32     no       78        ND   ND    ND    ND                                        yes      80        1.4  16.3   1.1   6.5                               33     no       75        ND   ND    ND    ND                                        yes      77        1.4  16.7   3.9  11.6                               34     no       73        ND   ND    ND    ND                                        yes      75        1.7  20.2   6.7  20.0                               35     no       82        0.9  14.0   0.6   6.0                                      yes      82        ND   ND    ND    ND                                 CE 1** no       59        2.2  19.3   9.2  27.2                                      yes      61        1.7  19.6   7.2  18.6                               37     no       64        2.0  23.3   0.5   3.8                                      yes      66        1.7  18.8   0.3   2.1                               38     no       61        2.7  25.5  13.1  24.0                                      yes      62        2.6  23.4  10.2  19.7                               39     no       58        3.1  29.3  24.0  33.1                                      yes      59        3.0  28.4  20.4  30.4                               40     no       58        3.6  40.8  34.3  51.1                                      yes      58        3.6  36.3  25.9  43.2                               41     no       51        3.1  43.0  40.1  54.6                                      yes      51        2.9  41.7  37.2  54.1                               42     no       53        2.8  41.6  33.8  54.4                                      yes      55        2.5  40.0  35.8  52.7                               43     no       61        2.1  26.5  16.5  27.8                                      yes      60        2.0  26.5  14.2  22.9                               44     no       61        3.3  31.1  25.7  36.9                                      yes      59        3.4  30.9  22.1  34.5                               45     no       58        3.1  36.4  32.4  46.4                                      yes      58        2.5  34.3  30.7  42.4                               46     no       46        3.9  63.0  61.8  67.3                                      yes      47        2.5  47.3  49.7  63.7                               ______________________________________                                         .sup. 1 Postcured at 175° C. for one hour                              .sup. 2 ASTM E140                                                             .sup. 3 Percent weight gain when soaked in a given solvent for 6 days at      ambient temperature                                                           *Not an example of the invention for reason stated in Table I                 ND = not determined                                                           **Comparative Example 1  not an example of this invention                

                  TABLE IIII                                                      ______________________________________                                        Impact Properties of Polymers Based on Backbone-Modified                      Diamines and Blends with D-2000                                                              Dynatup Impact                                                 Plaque                   Max           Energy to                              from   Post-    Notched  Force Energy to                                                                             Break                                  Example                                                                              Cured.sup.1                                                                            Izod.sup.2                                                                             (lb)  Max Force                                                                             (ft lb)                                ______________________________________                                        C*     no       3.1      600   4.8     5.3                                           yes      3.7      554   4.4     5.7                                    17     no       2.4      361   2.0     3.2                                           yes      1.9      624   4.5     6.4                                    18     no       0.4      174   0.2     0.4                                           yes      0.4      298   0.6     0.9                                    19     no       2.0      358   2.1     4.9                                           yes      2.0      400   2.2     5.4                                    20     no       2.0      120   0.4     0.6                                           yes      2.5      400   4.3     5.2                                    22     no       2.3      264   1.3     1.6                                           yes      2.5      464   3.2     5.7                                    23     no       2.2      296   1.4     1.6                                           yes      2.0      521   3.8     7.0                                    24     no       1.5      262   0.8     1.0                                           yes      1.9      505   3.5     6.3                                    25     no       0.3      229   0.3     0.6                                           yes      0.4      425   0.8     1.1                                    28     no       TB        46    0.05    0.08                                         yes      0.3      106    0.15    0.23                                  29     no       ND        44    0.06    0.09                                  30     no       0.5       68    0.13    0.18                                         yes      0.5      100    0.25    0.34                                  CE 1** no       2.2      435   3.4     4.4                                           yes      2.2      594   4.9     5.9                                    32     no       ND       628   5.0     5.3                                           yes      1.9      603   4.7     5.4                                    33     no       ND       450   2.8     3.1                                           yes      1.9      435   3.0     4.6                                    34     no       2.6      261   1.4     1.6                                           yes      2.4      702   6.4     6.9                                    35     no       0.4      351   0.6     0.9                                           yes      0.4      585   1.5     2.0                                    36     no       ND       ND    ND      ND                                            yes      1.7      625   3.2     3.8                                    37     no       0.3       85   0.2     0.2                                           yes      0.5      163   0.5     0.5                                    38     no       1.5      125   1.4     1.7                                           yes      1.7      450   4.3     5.1                                    39     no       2.2      137   0.7     0.9                                           yes      2.2      440   5.0     5.6                                    40     no       2.3       90   0.5     0.7                                           yes      3.1      190   1.3     1.5                                    41     no       2.0      132   1.0     1.2                                           yes      1.8      176   1.4     1.6                                    42     no       2.4      146   0.9     1.0                                           yes      2.2      120   0.7     0.9                                    43     no       2.1      120   1.4     2.0                                           yes      2.5      325   2.2     3.4                                    44     no       1.8       70   0.1     0.2                                           yes      2.8      795   8.5     9.2                                    45     no       1.8       90   0.4     0.5                                           yes      2.4      405   3.5     3.8                                    46     no       1.9      247   2.6     2.9                                           yes      1.8      225   2.1     2.5                                    ______________________________________                                         .sup.1 Postcured at 175° C. for one hour                               .sup.2 ASTM D256 (ambient temperature)                                        *Not an example of the invention for the reason stated in Table I             **Comparative Example 1  not an exammple of this invention                    TB = too brittle                                                              ND = not determined                                                      

Example 64

Reaction Product of Diamine Containing Four Urea Moieties in itsBackbone with ε-Caprolactone; ε-Caprolactone:Diamine; 4:1 Molar Ratio

A diamine containing 4 urea moieties per average backbone moleculesimilar to that prepared in Example 1A(12) (192.5 g, 0.9767 mole,MW=2510) and ε-caprolactone (35.02 g, 0.307 mole) are combined in thesame reaction setup used in Example 50. The reactor is heated at 180° C.for 6 hours. The product is obtained as a viscous liquid: Brookfieldviscosity=142,800 cps at 22° C.; 0.0714 meq amine/g by titration with0.1 N HClO₄ ; 89.4 percent amine conversion: calculated averagemolecular weight is 2966 by end group titration. Carbon-13 NMR (DMSO-d₆)shows amide carbonyl moieties (171 8 ppm), ester carbonyl moieties(173.1 ppm) and urea carbonyl moieties (157.5 ppm).

This example shows the preparation of a product which contains internalurea moieties in its backbone. A small amount of amino end groups(approx. 10 percent) are still present. There has been a substantialamount of further reaction to hydroxyl end groups linked by estermoieties (approx. 52:48 ester:amide moieties). Hydroxyl end groupslinked by ester moieties account for the majority of the product.

Example 65

Preparation of an Isocyanate Functional Prepolymer Comprised of Isonate™143LM and a 90/10 Weight Blend of Voranol™ 2120 and a Four Urea DiamineCapped with s-Caprolactone

A silanized, 100-ml resin kettle with a four-necked top is equipped witha mechanical stirrer, thermometer, vacuum inlet and a pressureequalizing addition funnel capped with a rubber septum. The kettle isheated to 55° C. in an oil bath and then charged with 5.36 g (0.0036equivalent) of the material made in Example 64 of disclosure D-35,787and 39.97 g (0.2693 equivalent) of Isonate™ 143LM carbodiimide-modifieddiisocyanate (a version of Isonate™ 143L which has a high percentage ofthe para-para isomer). The stirrer is then started and the kettle isplaced under a vacuum of 0.5 mm Hg. Voranol™ 2120 (a 2000 MWpolypropylene glycol, sold by The Dow Chemical Company) (44.50 g, 0.0441equivalent) is charged to the addition funnel through the septum via asyringe. The Voranol™ 2120 is then added dropwise to the kettle over a45-minute period while the stirring and vacuum are maintained.

After a reaction time of approximately 4 hours, a standardHCl/di-n-butylamine titration (ASTM D-1638-78) is done to determine theprepolymer's equivalent weight. The prepolymer's equivalent weight is416.72 g/equivalent with an NCO content of 10.08 weight percent.

Example 66

Preparation of a Polymer Based on 1,4-Butanediol and the Prepolymer Madein Example 65

The reaction setup and equipment are used that were used in Example 65.1,4-Butanediol (9.33 g, 0.2071 equivalent) are added to the prepolymerthrough the septum via a syringe. The mixture is stirred under vacuumfor 1.75 minutes and is then poured into a 4"×4"×0.125" steel windowmold lined with mylar sheets. The mold is then closed and placed in a150° C. oven for one hour after which it is removed and allowed to coolbefore being opened. The amount of 1,4-butanediol added is calculated togive a hard segment content of 50 weight percent. The Index (ratio ofisocyanate groups to hydroxyl groups) is 1.03.

After being removed from the mold, the plaque is post-cured at 150° C.for one hour in a vacuum oven and cut apart for testing. Test resultsare given hereinbelow.

What is claimed is:
 1. A modified polyamine comprising a backbone portion containing at least one polyalkyleneoxy moiety and one or more internal biuret, thiourea, dithiobiuret, or thioamide moieties, and a plurality of primary amino groups wherein each amino group is separated from each biuret, thiourea, dithiobiuret, or thioamide moiety by at least one alkylene, cycloalkylene, aralkylene, arylene, or alkyleneoxy moiety with 4-20 carbon atoms, or at least one polyalkyleneoxy moiety containing from 2-50 alkyleneoxy units.
 2. The modified polyamine of claim 1 which contains at least one internal biuret moiety.
 3. The modified polyamine of claim 1 which contains at least one internal thiourea moiety.
 4. The modified polyamine of claim 1 which contains at least one internal dithiobiuret moiety.
 5. The modified polyamine of claim 1 which contains at least one internal thioamide moiety.
 6. The modified polyamine of claim 1 represented by the formula:

    NH.sub.2 --R--[X--R].sub.n --NH.sub.2                      I

wherein each R is independently in each occurrence an alkylene, cycloalkylene, aralkylene, aryl, alkyleneoxy, or polyalkyleneoxy moiety, wherein at least one R is polyalkyleneoxy; X is independently in each occurrence an acyclic moiety selected from the group consisting of urea, biuret, thiourea, dithiobiuret, amide, and thioamide; and n is an integer between 1 and
 50. 7. A modified polyamine with a molecular weight of at least about 2000 comprising a backbone portion containing at least one polyalkyleneoxy moiety and two or more internal urea moieties, and a plurality of primary amino groups wherein each amino group is separated from each urea moiety by at least one alkylene, cycloalkylene, aralkylene, arylene, or alkyleneoxy moiety with 4-20 carbon atoms, or at least one polyalkyleneoxy moiety containing from 2-50 alkyleneoxy units.
 8. A modified polyamine comprising a backbone portion containing at least one polyalkyleneoxy moiety and at least two aminocarbonyl moieties different from each other which two moieties are selected from the group consisting of urea, biuret, thiourea, dithiobiuret, thioamide and amide wherein each amino group is separated from each aminocarbonyl moiety by at least one alkylene, cycloalkylene, aralkylene, arylene, or alkyleneoxy moiety with 4-20 carbon atoms, or at least one polyalkyleneoxy moiety with 2-50 alkyleneoxy units.
 9. A process for preparing a modified polyamine containing at least one internal biuret or dithiobiuret moiety which comprises contacting a polyalkyleneoxy polyamine with biuret or dithiobiuret under reaction conditions sufficient to form the corresponding modified polyamine containing at least one internal biuret or dithiobiuret moiety.
 10. A process for preparing an active hydrogen-containing compound with hydroxyl end groups which comprises contacting the modified polyamine of claim 1 with a cyclic lactone under reaction conditions sufficient to form the corresponding modified active hydrogen-containing compound with at least one hydroxyl end group.
 11. An active hydrogen-containing compound comprising a backbone portion containing at least one polyalkyleneoxy moiety and one or more internal urea, biuret, thiourea, dithiobiuret, amide or thioamide moieties, and a plurality of primary amino end groups and at least one hydroxyl end group, wherein each amino or hydroxyl end group is separated from each urea, biuret, thiourea, dithiobiuret, amide or thioamide moiety by at least one alkylene, cycloalkylene, aralkylene, arylene, or alkyleneoxy moiety with 4-20 carbon atoms, or at least one polyalkyleneoxy moiety containing from 2-50 alkyleneoxy units. 